EP3260419B1 - Surface-reacted calcium carbonate as extrusion aid - Google Patents
Surface-reacted calcium carbonate as extrusion aid Download PDFInfo
- Publication number
- EP3260419B1 EP3260419B1 EP16176267.9A EP16176267A EP3260419B1 EP 3260419 B1 EP3260419 B1 EP 3260419B1 EP 16176267 A EP16176267 A EP 16176267A EP 3260419 B1 EP3260419 B1 EP 3260419B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- calcium carbonate
- polysaccharide
- mpa
- extrusion aid
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims description 246
- 238000001125 extrusion Methods 0.000 title claims description 72
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims description 59
- 239000000463 material Substances 0.000 claims description 122
- 239000000203 mixture Substances 0.000 claims description 95
- 150000004676 glycans Chemical class 0.000 claims description 89
- 229920001282 polysaccharide Polymers 0.000 claims description 89
- 239000005017 polysaccharide Substances 0.000 claims description 89
- 238000000034 method Methods 0.000 claims description 83
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 77
- -1 H3O+ ion Chemical class 0.000 claims description 58
- 239000002253 acid Substances 0.000 claims description 58
- 235000013339 cereals Nutrition 0.000 claims description 51
- 229920002678 cellulose Polymers 0.000 claims description 39
- 239000001913 cellulose Substances 0.000 claims description 38
- 235000013305 food Nutrition 0.000 claims description 38
- 239000000725 suspension Substances 0.000 claims description 33
- 240000008042 Zea mays Species 0.000 claims description 28
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 28
- 235000013312 flour Nutrition 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 159000000007 calcium salts Chemical class 0.000 claims description 19
- 235000011888 snacks Nutrition 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 244000075850 Avena orientalis Species 0.000 claims description 16
- 235000007319 Avena orientalis Nutrition 0.000 claims description 16
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- 235000009973 maize Nutrition 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000004438 BET method Methods 0.000 claims description 9
- 240000005979 Hordeum vulgare Species 0.000 claims description 9
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- 240000006162 Chenopodium quinoa Species 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 244000062793 Sorghum vulgare Species 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 8
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- 239000004579 marble Substances 0.000 claims description 8
- 235000019713 millet Nutrition 0.000 claims description 8
- 235000020985 whole grains Nutrition 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 241001465754 Metazoa Species 0.000 claims description 6
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- 229920000869 Homopolysaccharide Polymers 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 5
- 239000006028 limestone Substances 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 235000015496 breakfast cereal Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
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- 239000010459 dolomite Substances 0.000 claims description 2
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- 235000010216 calcium carbonate Nutrition 0.000 description 53
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- 239000011148 porous material Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 25
- 238000002156 mixing Methods 0.000 description 15
- 239000000523 sample Substances 0.000 description 14
- 239000007858 starting material Substances 0.000 description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 239000007900 aqueous suspension Substances 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
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- 238000009826 distribution Methods 0.000 description 8
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- 239000002002 slurry Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 238000002459 porosimetry Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
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- 239000000796 flavoring agent Substances 0.000 description 3
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- 150000004677 hydrates Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011785 micronutrient Substances 0.000 description 1
- 235000013369 micronutrients Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
- A23L7/10—Cereal-derived products
- A23L7/161—Puffed cereals, e.g. popcorn or puffed rice
- A23L7/165—Preparation of puffed cereals involving preparation of meal or dough as an intermediate step
- A23L7/17—Preparation of puffed cereals involving preparation of meal or dough as an intermediate step by extrusion
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
- A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
- A23L29/262—Cellulose; Derivatives thereof, e.g. ethers
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/294—Inorganic additives, e.g. silica
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P30/00—Shaping or working of foodstuffs characterised by the process or apparatus
- A23P30/30—Puffing or expanding
- A23P30/32—Puffing or expanding by pressure release, e.g. explosion puffing; by vacuum treatment
- A23P30/34—Puffing or expanding by pressure release, e.g. explosion puffing; by vacuum treatment by extrusion-expansion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/463—Edible packaging materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
- C09C1/022—Treatment with inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- the present application relates to the use of surface-reacted calcium carbonate as extrusion aid for the production of puffed polysaccharide-based materials.
- Puffed polysaccharide-based materials obtained by means of extrusion cooking are very often used as or processed into food products for human consumption (e.g. breakfast cereals or snacks) or for animal consumption (e.g. pet food).
- human consumption e.g. breakfast cereals or snacks
- animal consumption e.g. pet food
- the use of these polysaccharide-based materials is also common for non-food applications, particularly for packaging materials.
- Suitable starting materials thus include groat, semolina or flour of barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet and the like.
- the ground starting material is fed to the inlet of an extruder and then heated to temperatures of 100°C or higher. After leaving the extruder through a die, water and other volatiles contained in the starting material evaporate immediately which is associated with a cross-sectional or volume expansion of the extrudate. Said expansion may be described by the so-called expansion index F , wherein a high expansion index indicates a higher porosity and a lower density of the extrudate.
- pluri or “puffed” as used throughout this application refer to the property of a solid material providing the skeletal construct of a porous or foamy structure obtained through porous expansion of a suitable starting formulation.
- expansion is achieved by evaporation of a liquid (e.g. water) embedded in said starting formulation using elevated temperatures and/or rapid pressure decrease.
- a liquid e.g. water
- US2009/0291179 A1 and US2012/0064209 A1 disclose methods for manufacturing extruded snack products, using calcium carbonate as an expansion controlling agent. Accordingly, there is still a need for the provision of improved extrusion cooked puffed materials and improved processes for their production.
- One object of the present invention may therefore be seen in the provision of puffed extrusion cooked materials with an increased expansion index.
- Another object may be seen in the provision of puffed extrusion cooked food products with improved crispness.
- Still another object may be seen in the provision of a puffed extrudate having a smoother or more uniform texture.
- Still another object may be seen in the provision of a puffed extrudate with increased hardness.
- increased hardness may positively affect the mouthfeel.
- increased hardness is associated with improved stability and safety of transported goods.
- Still another object may be seen in the provision of a material and cost saving process for the production of puffed polysaccharide-based materials.
- a first aspect of the present invention relates to a process for the production of a puffed polysaccharide-based material, the process comprising the following steps:
- a mixture comprising a suitable puffable material and surface-reacted calcium carbonate are subjected to an extrusion step, i.e. at elevated temperatures and elevated pressure.
- Suitable puffable materials may be, for example, groat, semolina or flour of barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet and the like excluding fibrillated cellulose-containing materials (i.e.
- the surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC) treated with CO 2 and one or more H 3 O + ion donors. While not wishing to be bound by any theory, it is believed that the surface-reacted calcium carbonate serves as a so-called "bubble nucleating agent" which provides large surfaces and enhances or accelerates the evaporation of liquids, such as water, contained in the raw mixture at the outlet of the extruder.
- GNCC ground natural calcium carbonate
- PCC precipitated calcium carbonate
- Improved characteristics of the puffed extrudate obtainable by means of the inventive process include increased expansion indices, which may be used to describe the cross-sectional or volume expansion of the extrudate after passing the outlet of an extruder. Further to this, the products obtainable according to the inventive extrusion process were found to provide improved results in organoleptic panel testing, for example improved crispness or a more uniform surface.
- Another aspect of the present invention relates to the use of a surface-reacted calcium carbonate as extrusion aid for the production of a puffed polysaccharide-based material excluding fibrillated cellulose-containing materials, wherein the surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC) treated with CO 2 and one or more H 3 O + ion donors and wherein the CO 2 is formed in situ by the H 3 O + ion donors treatment and/or is supplied from an external source.
- GNCC ground natural calcium carbonate
- PCC precipitated calcium carbonate
- Still another aspect of the present invention relates to a puffed polysaccharide-based material excluding fibrillated cellulose-containing materials, obtainable according to the inventive process.
- solid refers to a physical state of a material. Unless indicated otherwise, this physical state is to be observed at a temperature of 20°C.
- surface-reacted e.g. surface-reacted GNCC or PCC
- surface-reacted GNCC or PCC in the meaning of the present application shall be used to indicate that a material has been subjected to a process comprising partial dissolution of said material upon acidic treatment (e.g., by use of water soluble free acids and/or acid salts) in an aqueous environment followed by a crystallization process which may occur in the absence or presence of further crystallization additives.
- acid refers to an acid in the meaning of the definition by Bronsted and Lowry (e.g. H 2 SO 4 , HSO 4 - ).
- a "surface-reacted" material may be characterized by an increased intraparticle intruded specific pore volume as compared to the untreated starting material (i.e. GNCC or PCC). Said increased pore volume or porosity is a result of the dissolution and recrystallisation process during its formation. Usually, the starting materials do not show any or only low internal porosity.
- the polysaccharide is a homopolysaccharide and preferably is starch; and/or (ii) the polysaccharide-containing ground material provided in step (a) comprises barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof, preferably the polysaccharide-containing ground material is selected from groat, semolina or flour of barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof, and more preferably the polysaccharide-containing ground material is corn (maize) flour, wheat flour, nut flour or a mixture thereof.
- the one or more H 3 O + ion donors are selected from (i) strong acids having a pK a of 0 or less at 20°C; and/or (ii) medium-strong acids having a pK a value from 0 to 2.5 at 20°C; and/or (iii) weak acids having a pK a of greater than 2.5 and less than or equal to 7 at 20°C, associated with the ionisation of its first available hydrogen, wherein a corresponding anion is formed on loss of this first available hydrogen capable of forming a water-soluble calcium salt, and wherein at least one water-soluble salt, which in the case of a hydrogen-containing salt has a pK a of greater than 7 at 20°C, associated with the ionisation of the first available hydrogen, and the salt anion of which is capable of forming water-insoluble calcium salts, is additionally provided.
- the surface-reacted calcium carbonate is obtained by a process comprising the following steps:
- the surface-reacted calcium carbonate is obtained by a process comprising the following steps:
- the natural calcium carbonate is selected from the group consisting of marble, chalk, dolomite, limestone and mixtures thereof; and/or (ii) the precipitated calcium carbonate comprises aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof.
- the extrusion aid has (i) a volume median grain diameter d 50 (vol) of from 1 to 75 ⁇ m, preferably from 1.5 to 50 ⁇ m, more preferably from 2 to 40 ⁇ m, and most preferably from 2.5 to 7.0 ⁇ m; and/or (ii) a volume grain diameter d 98 (vol) of from 2 to 150 ⁇ m, preferably from 4 to 100 ⁇ m, more preferably from 6 to 80 ⁇ m, even more preferably from 8 to 60 ⁇ m, and most preferably from 10 to 30 ⁇ m.
- the extrusion aid has a specific surface area of from 15 to 200 m 2 /g, preferably from 27 to 180 m 2 /g, more preferably from 30 to 160 m 2 /g, even more preferably from 45 to 150 m 2 /g, and most preferably from 48 to 140 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:1995.
- the mixture obtained in step (c) comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of the extrusion aid provided in step (b), based on the total dry weight of said mixture.
- step (i) the mixture obtained in step (c) is heated to from 100°C to 150°C, preferably from 105°C to 140°C, more preferably from 110°C to 135°C, and most preferably from 115°C to 130°C; and/or (ii) the extruder operates at a minimum pressure of 0.5 MPa, preferably 2.5 MPa, more preferably 3.5 MPa, even more preferably 5 MPa, even more preferably 5.5 MPa, and most preferably 6 MPa; and/or (iii) the extruder operates at a maximum pressure of 10 MPa, preferably 8 MPa, more preferably 7.5 MPa, even more preferably 6 MPa, and most preferably 5 MPa.
- the mixture obtained in step (c) further comprises the following additives: (i) water, preferably in amount of from 0.01 to 15 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%; and/or (ii) whole grains, preferably in amount of from 0.1 to 30 wt.-%, more preferably from 0.5 to 20 wt.-%, and most preferably from 1 to 15 wt.-%; and/or (iii) sucrose, preferably in amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%; and/or (iv) sodium chloride, preferably in amount of from 0.001 to 5 wt.-%, more preferably from 0.01 to 2 wt.-%, and most preferably from 0.1 to 1 wt.-%; each additives: (i) water,
- the process further comprises step (e) of processing the puffed polysaccharide-based extrudate obtained in step (d) into: (i) a food product for human consumption, preferably breakfast cereals and/or snacks; or (ii) a food product for animal consumption, preferably pet food, and more preferably fish food, bird food, dog food and/or cat food; or (iii) a packaging material.
- the puffed polysaccharide-based material obtainable according to the inventive process provides: (i) an expansion index F of from 5 to 30, preferably from 8 to 25, more preferably from 10 to 20, and most preferably from 12 to 18; and/or (ii) a crispness of from 25 to 50 N, preferably from 30 to 48 N, more preferably from 32 to 45 N, and most preferably from 35 to 40 N, measured on a TA.HDplus Texture Analyser from Stable Micro Systems equipped with a Kramer Shear cell with 10 blades.
- the base material used in the extrusion process according to the present invention is a polysaccharide-containing ground material, excluding fibrillated cellulose-containing materials (i.e. materials containing microfibrillated cellulose, materials containing nanofibrillated cellulose, materials containing nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill), and is provided in step (a).
- fibrillated cellulose-containing materials i.e. materials containing microfibrillated cellulose, materials containing nanofibrillated cellulose, materials containing nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill
- polysaccharide in the meaning of the present invention is understood to be a polymeric carbohydrate composed of long chains of monosaccharide units, preferably 10 or more units, bound together by glycosidic linkages, excluding fibrillated cellulose.
- Typical examples of polysaccharides include glycogen, starch, pectines, chitin, callose, or cellulose excluding fibrillated cellulose.
- polysaccharide shall not include fibrillated cellulose in any of the aspects and embodiments disclosed in the present application.
- fibrillated cellulose as used herein is a collective referring to both micro- and nanofibrillated cellulose, nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill.
- microfibrillation The breakdown of fibres into isolated microfibrils is referred to as "microfibrillation”. This process may be continued until there are no fibres left and only elementary or primary fibrils remain which have a nanosized diameter. The foregoing breakdown of fibres into isolated elementary or primary fibrils is referred to as "nanofibrillation”.
- microfibrillated cellulose in the context of the present invention relates to a plurality of fibres, which is at least partially broken down to microfibrils, preferably microfibrillated cellulose is essentially free or free of isolated primary or elementary fibrils.
- nanofibrillated cellulose relates to a plurality of fibres, which is at least partially broken down to primary or elementary fibrils, preferably nanofibrillated cellulose is essentially free or free of isolated microfibrils.
- a material is "essentially” free of a specific substance if the amount of that substance may vary within a certain tolerable range without deviating from the basic concept underlying the present invention.
- a material is "essentially” free of a specific substance if it contains less than 10 wt.-% of that substance, more preferably less than 5 wt.-% and most preferably less than 1 wt.-%, based on the total dry weight of said material.
- the polysaccharide is a homopolysaccharide meaning that the polysaccharide is composed of a plurality of identical monosaccharide units.
- the product obtained according to the present invention is a puffed homopolysaccharide-based material.
- the monosaccharide is selected from glucose and/or fructose.
- suitable glucose or fructose homopolysaccharides thus include starch, glycogen, callose, cellulose excluding fibrillated cellulose, and inulin.
- a particularly preferred (homo-)polysaccharide is starch.
- Starch is a homopolymer of glucose and is used as a storage polysaccharide in plants, being found in the form of both amylose and the branched amylopectin.
- starch refers to a mixture of amylose and amylopectin unless indicated otherwise.
- Suitable polysaccharide-containing materials are cereals.
- the polysaccharide-containing ground material therefore is a ground cereal.
- said cereal is selected from barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof. If cereals are used as the polysaccharide-containing material, it is in principle possible to use both ground whole grains and ground refined grains to provide the polysaccharide-containing ground material of step (a).
- the polysaccharide-containing ground material is therefore selected from ground whole grain cereals or ground refined grain cereals.
- the polysaccharide-containing ground material is a ground refined grain cereal.
- the product obtainable according to the inventive process is a puffed material, meaning that it has an expanded porous or foamy structure which is caused by evaporation of a liquid (e.g. water) embedded in the polysaccharide-containing starting material by applying elevated temperatures and/or rapid pressure decrease.
- a liquid e.g. water
- at least part of the starting material provided in step (a) is a ground material in order to ensure that the extrusion aid is in contact with the polysaccharide.
- the ground material provided in step (a) may in principle have any grinding degree, i.e. it may be finely ground or coarsely ground.
- the polysaccharide-containing ground material is provided in the form of groat, semolina or flour.
- the polysaccharide-containing ground material is provided in the form of flour. Therefore, a preferred embodiment of the inventive process uses cereal flour as the polysaccharide-containing ground material.
- non-cereal flours from other polysaccharide sources may be used such as, for example, potato flour, tapioca flour, nut-flour or mixtures thereof.
- nut flour are almond, coconut, hazelnut, pecan, and macadamia flour or mixtures thereof.
- the polysaccharide-containing ground material is selected from groat, semolina or flour of the following suitable cereals: barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof. More preferably, the polysaccharide-containing ground material is corn (maize) flour, wheat flour, nut flour or a mixture thereof.
- step (a) it may be sufficient if at least part of the starting material in step (a) is provided as a ground material. Therefore, it is also possible to use a mixture of ground materials, for example any of the flours described hereinabove, and whole grains.
- the polysaccharide-containing ground material provided in step (a) may contain water or other evaporable liquids. In case of using ground cereals or other starch-containing ground materials, the polysaccharide-containing ground material naturally contains water. In some embodiments, the polysaccharide-containing ground material provided in step (a) contains water in an amount of from 0.05 to 50 wt.-%, preferably from 0.1 to 40 wt.-%, more preferably from 0.5 to 30 wt.-%, and most preferably from 1 to 25 wt.-%, based on the total weight of the polysaccharide-containing ground material.
- the extrusion aid defined in step (b) of the inventive process is a surface-reacted calcium carbonate (SRCC).
- SRCC surface-reacted calcium carbonate
- FCC functionalized calcium carbonate
- the surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate or precipitated calcium carbonate treated with CO 2 and one or more H 3 O + ion donors, wherein the CO 2 is formed in situ by the H 3 O + ion donors treatment and/or is supplied from an external source.
- An H 3 O + ion donor in the context of the present invention is a Bronsted acid and/or an acid salt.
- the surface-reacted calcium carbonate is obtained by a process comprising the steps of:
- the surface-reacted calcium carbonate is obtained by a process comprising the steps of:
- the source of calcium carbonate e.g. "ground natural calcium carbonate” (GNCC)
- GNCC ground natural calcium carbonate
- natural calcium carbonate may comprise further naturally occurring components such as magnesium carbonate, alumino silicate etc.
- the grinding of ground natural calcium carbonate may be performed in a dry or wet grinding process and may be carried out with any conventional grinding device, for example, under conditions such that comminution predominantly results from impacts with a secondary body, i.e. in one or more of: a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled person.
- a ball mill a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled person.
- a secondary body
- the grinding step may be performed under conditions such that autogenous grinding takes place and/or by horizontal ball milling, and/or other such processes known to the skilled person.
- the wet processed ground natural calcium carbonate thus obtained may be washed and dewatered by well-known processes, e.g. by flocculation, filtration or forced evaporation prior to drying.
- the subsequent step of drying (if necessary) may be carried out in a single step such as spray drying, or in at least two steps. It is also common that such a mineral material undergoes a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities.
- a "precipitated calcium carbonate” (PCC) in the meaning of the present invention is a synthesized material, generally obtained by precipitation following a reaction of CO 2 and calcium hydroxide in an aqueous environment or by precipitation of calcium and carbonate ions, for example CaCl 2 and Na 2 CO 3 , out of solution.
- Further possible ways of producing PCC are the lime soda process, or the Solvay process in which PCC is a by-product of ammonia production.
- Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and vaterite, and there are many different polymorphs (crystal habits) for each of these crystalline forms.
- Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC).
- Aragonite is an orthorhombic structure with typical crystal habits of twinned hexagonal prismatic crystals, as well as a diverse assortment of thin elongated prismatic, curved bladed, steep pyramidal, chisel shaped crystals, branching tree, and coral or worm-like form.
- Vaterite belongs to the hexagonal crystal system.
- the obtained PCC slurry can be mechanically dewatered and dried.
- the precipitated calcium carbonate is precipitated calcium carbonate, preferably comprising aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof.
- Precipitated calcium carbonate may be ground prior to the treatment with CO 2 and at least one H 3 O + ion donor by the same means as used for grinding natural calcium carbonate and described above.
- the natural or precipitated calcium carbonate is in form of particles having a weight median particle size dso(wt) of from 0.05 to 10.0 ⁇ m, preferably from 0.2 to 5.0 ⁇ m, more preferably from 0.4 to 3.0 ⁇ m, most preferably from 0.6 to 1.2 ⁇ m, and especially 0.7 ⁇ m.
- the natural or precipitated calcium carbonate is in form of particles having a top cut particle size d 98 (wt) of from 0.15 to 55 ⁇ m, preferably from 1 to 40 ⁇ m, more preferably from 2 to 25 ⁇ m, most preferably from 3 to 15 ⁇ m, and especially 4 ⁇ m.
- the value d x represents the diameter relative to which x % of the particles have diameters less than d x .
- the d 98 value is also designated as "top cut”.
- the d x values may be given in volume or weight percent.
- the d 50 (wt) value is thus the "weight median particle size", i.e. 50 wt.-% of all grains are smaller than this particle size, and the d 50 (vol) value is the "volume median particle size", i.e. 50 vol.-% of all grains are smaller than this particle size.
- the natural and/or precipitated calcium carbonate may be used dry or suspended in water.
- a corresponding slurry has a content of natural or precipitated calcium carbonate within the range of from 1 to 90 wt.-%, more preferably from 3 to 60 wt.-%, even more preferably from 5 to 40 wt.-%, and most preferably from 10 to 25 wt.-%, based on the total weight of the slurry.
- the one or more H 3 O + ion donor used for the preparation of surface reacted calcium carbonate may be any strong acid, medium-strong acid, or weak acid, or mixtures thereof, generating H 3 O + ions under the preparation conditions.
- the at least one H 3 O + ion donor can also be an acid salt, generating H 3 O + ions under the preparation conditions.
- the at least one H 3 O + ion donor is a strong acid having a pK a of 0 or less at 20°C.
- the at least one H 3 O + ion donor is a medium-strong acid having a pK a value from 0 to 2.5 at 20°C. If the pK a at 20°C is 0 or less, the acid is preferably selected from sulphuric acid, hydrochloric acid, or mixtures thereof. If the pK a at 20°C is from 0 to 2.5, the H 3 O + ion donor is preferably selected from H 2 SO 3 , H 3 PO 4 , oxalic acid, or mixtures thereof.
- the at least one H 3 O + ion donor can also be an acid salt, for example, HSO 4 - or H 2 PO 4 - , being at least partially neutralized by a corresponding cation such as Li + , Na + or K + , or HPO 4 2- , being at least partially neutralised by a corresponding cation such as Li + , Na + ' K + , Mg 2+ or Ca 2+ .
- the at least one H 3 O + ion donor can also be a mixture of one or more acids and one or more acid salts.
- the at least one H 3 O + ion donor is a weak acid having a pK a value of greater than 2.5 and less than or equal to 7, when measured at 20°C, associated with the ionisation of the first available hydrogen, and having a corresponding anion, which is capable of forming water-soluble calcium salts.
- at least one water-soluble salt which in the case of a hydrogen-containing salt has a pK a of greater than 7, when measured at 20°C, associated with the ionisation of the first available hydrogen, and the salt anion of which is capable of forming water-insoluble calcium salts, is additionally provided.
- the weak acid has a pK a value from greater than 2.5 to 5 at 20°C, and more preferably the weak acid is selected from the group consisting of acetic acid, formic acid, propanoic acid, and mixtures thereof.
- Exemplary cations of said water-soluble salt are selected from the group consisting of potassium, sodium, lithium and mixtures thereof. In a more preferred embodiment, said cation is sodium or potassium.
- Exemplary anions of said water-soluble salt are selected from the group consisting of phosphate, dihydrogen phosphate, monohydrogen phosphate, oxalate, silicate, mixtures thereof and hydrates thereof.
- said anion is selected from the group consisting of phosphate, dihydrogen phosphate, monohydrogen phosphate, mixtures thereof and hydrates thereof. In a most preferred embodiment, said anion is selected from the group consisting of dihydrogen phosphate, monohydrogen phosphate, mixtures thereof and hydrates thereof.
- Water-soluble salt addition may be performed dropwise or in one step. In the case of drop wise addition, this addition preferably takes place within a time period of 10 minutes. It is more preferred to add said salt in one step.
- the at least one H 3 O + ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid, and mixtures thereof.
- the at least one H 3 O + ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, H 2 PO 4 - , being at least partially neutralised by a corresponding cation such as Li + , Na + or K + , HPO 4 2- , being at least partially neutralised by a corresponding cation such as Li + , Na + ' K + , Mg 2+ , or Ca 2+ and mixtures thereof, more preferably the at least one acid is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, or mixtures thereof, and most preferably, the at least one H 3 O + ion donor is phosphoric acid.
- the one or more H 3 O + ion donor can be added to the suspension as a concentrated solution or a more diluted solution.
- the molar ratio of the H 3 O + ion donor to the natural or precipitated calcium carbonate is from 0.01 to 4, more preferably from 0.02 to 2, even more preferably from 0.05 to 1 and most preferably from 0.1 to 0.58.
- the natural or precipitated calcium carbonate is treated with CO 2 .
- a strong acid such as sulphuric acid or hydrochloric acid is used for the H 3 O + ion donor treatment of the natural or precipitated calcium carbonate, the CO 2 is automatically formed.
- the CO 2 can be supplied from an external source.
- H 3 O + ion donor treatment and treatment with CO 2 can be carried out simultaneously which is the case when a strong or medium-strong acid is used. It is also possible to carry out H 3 O + ion donor treatment first, e.g. with a medium strong acid having a pK a in the range of 0 to 2.5 at 20°C, wherein CO 2 is formed in situ, and thus, the CO 2 treatment will automatically be carried out simultaneously with the H 3 O + ion donor treatment, followed by the additional treatment with CO 2 supplied from an external source.
- the concentration of gaseous CO 2 in the suspension is, in terms of volume, such that the ratio (volume of suspension):(volume of gaseous CO 2 ) is from 1:0.05 to 1:20, even more preferably 1:0.05 to 1:5.
- the H 3 O + ion donor treatment step and/or the CO 2 treatment step are repeated at least once, more preferably several times.
- the at least one H 3 O + ion donor is added over a time period of at least about 5 min, preferably at least about 10 min, typically from about 10 to about 20 min, more preferably about 30 min, even more preferably about 45 min, and sometimes about 1 h or more.
- the pH of the aqueous suspension measured at 20°C, naturally reaches a value of greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5, thereby preparing the surface-reacted natural or precipitated calcium carbonate as an aqueous suspension having a pH of greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5.
- surface-reacted precipitated calcium carbonate may be obtained.
- surface-reacted precipitated calcium carbonate is obtained by contacting precipitated calcium carbonate with H 3 O + ions and with anions being solubilized in an aqueous medium and being capable of forming water-insoluble calcium salts, in an aqueous medium to form a slurry of surface-reacted precipitated calcium carbonate, wherein said surface-reacted precipitated calcium carbonate comprises an insoluble, at least partially crystalline calcium salt of said anion formed on the surface of at least part of the precipitated calcium carbonate.
- Said solubilized calcium ions correspond to an excess of solubilized calcium ions relative to the solubilized calcium ions naturally generated on dissolution of precipitated calcium carbonate by H 3 O + ions, where said H 3 O + ions are provided solely in the form of a counter ion to the anion, i.e. via the addition of the anion in the form of an acid or non-calcium acid salt, and in absence of any further calcium ion or calcium ion generating source.
- Said excess solubilized calcium ions are preferably provided by the addition of a soluble neutral or acid calcium salt, or by the addition of an acid or a neutral or acid non-calcium salt which generates a soluble neutral or acid calcium salt in situ.
- Said H 3 O + ions may be provided by the addition of an acid or an acid salt of said anion, or the addition of an acid or an acid salt which simultaneously serves to provide all or part of said excess solubilized calcium ions.
- the natural or precipitated calcium carbonate is reacted with the acid and/or the CO 2 in the presence of at least one compound selected from the group consisting of silicate, silica, aluminium hydroxide, earth alkali aluminate such as sodium or potassium aluminate, magnesium oxide, aluminium sulfate or mixtures thereof.
- the at least one silicate is selected from an aluminium silicate, a calcium silicate, or an earth alkali metal silicate.
- the silicate and/or silica and/or aluminium hydroxide and/or earth alkali aluminate and/or magnesium oxide component(s) can be added to the aqueous suspension of natural or precipitated calcium carbonate while the reaction of natural or precipitated calcium carbonate with an acid and CO 2 has already started. Further details about the preparation of the surface-reacted natural or precipitated calcium carbonate in the presence of at least one silicate and/or silica and/or aluminium hydroxide and/or earth alkali aluminate component(s) are disclosed in WO 2004/083316 A1 , the content of this reference herewith being included in the present application.
- the surface-reacted calcium carbonate can be kept in suspension, optionally further stabilised by a dispersant.
- a dispersant Conventional dispersants known to the skilled person can be used.
- a preferred dispersant is comprised of polyacrylic acids and/or carboxymethylcelluloses.
- the aqueous suspension described above can be dried, thereby obtaining the solid (i.e. dry or containing as little water that it is not in a fluid form) surface-reacted natural or precipitated calcium carbonate in the form of granules or a powder.
- the surface reacted calcium carbonate may have different particle shapes, such as, for example, the shape of roses, golf balls and/or brains.
- the extrusion aid has a specific surface area of from 15 to 200 m 2 /g, preferably from 27 to 180 m 2 /g, more preferably from 30 to 160 m 2 /g, even more preferably from 45 to 150 m 2 /g, and most preferably from 48 to 140 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:1995.
- the extrusion aid has a specific surface area of 120 m 2 /g or less, more preferably from 60 to 120 m 2 /g, and most preferably from 70 to 105 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:1995.
- the extrusion aid may have a specific surface area of from 75 to 100 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:1995.
- the extrusion aid has a volume median grain diameter d 50 (vol) of from 1 to 75 ⁇ m, preferably from 2 to 50 ⁇ m, more preferably from 3 to 40 ⁇ m, even more preferably from 4 to 30 ⁇ m, and most preferably from 5 to 15 ⁇ m.
- the extrusion aid has a volume median grain diameter d 50 (vol) of from 1.5 to 12 ⁇ m, preferably from 2 to 5 ⁇ m or from 6 to 10 ⁇ m.
- the extrusion aid has a grain diameter d 98 (vol) of from 2 to 150 ⁇ m, preferably from 4 to 100 ⁇ m, more preferably from 6 to 80 ⁇ m, even more preferably from 8 to 60 ⁇ m, and most preferably from 10 to 30 ⁇ m.
- the extrusion aid has a volume grain diameter d 98 (vol) of from 5 to 20 ⁇ m, preferably from 8 to 12 ⁇ m or from 13 to 18 ⁇ m.
- the extrusion aid is thus a surface-reacted ground natural calcium carbonate (GNCC) having: (i) a volume median grain diameter dso(vol) of from 1.5 to 12 ⁇ m, preferably from 2 to 5 ⁇ m or from 6 to 10 ⁇ m; and/or (ii) a volume grain diameter d 98 (vol) of from 5 to 20 ⁇ m, preferably from 8 to 12 ⁇ m or from 13 to 18 ⁇ m.
- GNCC surface-reacted ground natural calcium carbonate
- the extrusion aid is a surface-reacted ground natural calcium carbonate (GNCC) having: (i) a volume median grain diameter d 50 (vol) of from 1.5 to 12 ⁇ m, preferably from 2 to 5 ⁇ m or from 6 to 10 ⁇ m; and/or (ii) a volume grain diameter d 98 (vol) of from 5 to 20 ⁇ m, preferably from 8 to 12 ⁇ m or from 13 to 18 ⁇ m; and/or (iii) a specific surface area of 120 m 2 /g or less, more preferably from 60 to 120 m 2 /g, and most preferably from 70 to 105 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:1995.
- GNCC surface-reacted ground natural calcium carbonate
- the polysaccharide-containing ground material is selected from groat, semolina or flour of the following suitable cereals: barley, corn (maize), oats, rice, rye, spelt and wheat, preferably corn (maize) flour or wheat flour.
- the extrusion aid has an intra-particle intruded specific pore volume in the range from 0.1 to 2.3 cm 3 /g, more preferably from 0.2 to 2.0 cm 3 /g, especially preferably from 0.4 to 1.8 cm 3 /g and most preferably from 0.6 to 1.6 cm 3 /g, calculated from mercury porosimetry measurement.
- the intra-particle pore size of the extrusion aid preferably is in a range of from 0.004 to 1.6 ⁇ m, more preferably in a range of between 0.005 to 1.3 ⁇ m, especially preferably from 0.006 to 1.15 ⁇ m and most preferably of 0.007 to 1.0 ⁇ m, e.g. 0.004 to 0.50 ⁇ m determined by mercury porosimetry measurement.
- the specific pore volume can be measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter.
- the total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 214 ⁇ m down to about 1 to 4 ⁇ m showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine interparticle packing of the particles themselves. If they also have intraparticle pores, then this region appears bimodal, and by taking the specific pore volume intruded by mercury into pores finer than the modal turning point, i.e. finer than the bimodal point of inflection, we thus define the specific intraparticle pore volume. The sum of these three regions gives the total overall pore volume of the powder, but depends strongly on the original sample compaction/settling of the powder at the coarse pore end of the distribution.
- step (c) of the process according to the present invention the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) are combined to obtain an extrudable mixture.
- the polysaccharide-containing ground material provided in step (a) excludes fibrillated cellulose-containing materials.
- step (c) there exist two ways for preparing the mixture of step (c), namely separate feeding to the extruder and pre-mixing.
- the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) are fed separately to the extruder inlet, meaning that the raw mixture of step (c) comprising the polysaccharide-containing ground material and the extrusion aid is formed within the extruder.
- the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) are pre-mixed to obtain the mixture of step (c) which is then fed to the extruder inlet.
- any suitable mixing device known in the art may be used, for example a spiral kneader or a ploughshare mixer.
- a combination of separate feeding and pre-mixing may be used to obtain the mixture of step (c) comprising the polysaccharide-containing ground material and the extrusion aid.
- the major component of the mixture obtained in step (c), on a dry weights basis is the polysaccharide-containing ground material.
- the mixture obtained in step (c) comprises at least 70 wt.-%, preferably at least 80 wt.-%, and most preferably at least 85 wt.-% of polysaccharide-containing ground material, based on the total dry weight of said mixture.
- the mixture obtained in step (c) comprises from 60 to 99.5 wt.-%, more preferably from 70 to 98.5 wt.-%, and most preferably from 75 to 98 wt.-% of polysaccharide-containing ground material, based on the total dry weight of said mixture.
- the second important component in the raw mixture of step (c) is the extrusion aid which is a surface-reacted calcium carbonate.
- the mixture obtained in step (c) comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of said extrusion aid provided in step (b), based on the total dry weight of said mixture.
- the mixture obtained in step (c) comprises from 0.3 to 0.7 wt.-% or from 1.2 to 2.2 wt.-% of said extrusion aid provided in step (b), based on the total dry weight of said mixture.
- the extrusion aid of the foregoing embodiments is a surface-reacted ground natural calcium carbonate (GNCC) having: (i) a volume median grain diameter d 50 (vol) of from 1.5 to 12 ⁇ m, preferably from 2 to 5 ⁇ m or from 6 to 10 ⁇ m; and/or (ii) a volume grain diameter d 98 (vol) of from 5 to 20 ⁇ m, preferably from 8 to 12 ⁇ m or from 13 to 18 ⁇ m; and/or (iii) a specific surface area of 120 m 2 /g or less, more preferably from 60 to 120 m 2 /g, and most preferably from 70 to 105 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:1995.
- GNCC surface-reacted ground natural calcium carbonate
- the mixture obtained in step (c) may contain one or more suitable additives such as, for example, fillers, dispersants, lubricants, leavenings, nucleating agents, colorants, vitamins, antioxidants, fats, micro nutrients, or flavorants.
- suitable additives such as, for example, fillers, dispersants, lubricants, leavenings, nucleating agents, colorants, vitamins, antioxidants, fats, micro nutrients, or flavorants.
- the mixture obtained in step (c) further comprises added water, preferably in amount of from 0.01 to 15 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%, based on the total dry weight of said mixture. It should be noted that the total amount of water in the mixture obtained in step (c) may be higher than the amount of added water as both the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) may already contain water.
- the total water content of the mixture obtained in step (c) is therefore adjusted to from 0.5 to 70 wt.-%, preferably from 1 to 50 wt.-%, more preferably from 2 to 40 wt.-%, and most preferably from 5 to 30 wt.-%, based on the total weight of said mixture.
- the mixture obtained in step (c) further comprises added whole grains, preferably in amount of from 0.1 to 30 wt.-%, more preferably from 0.5 to 20 wt.-%, and most preferably from 1 to 15 wt.-%, based on the total dry weight of said mixture.
- the mixture obtained in step (c) further comprises added sucrose, preferably in amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%, based on the total dry weight of said mixture.
- the mixture obtained in step (c) further comprises sodium chloride, preferably in amount of from 0.001 to 5 wt.-%, more preferably from 0.01 to 2 wt.-%, and most preferably from 0.1 to 1 wt.-%, based on the total dry weight of said mixture.
- the mixture obtained in step (c) may also contain unmodified GNCC or PCC additives, i.e. calcium carbonates which are not surface-reacted. Moreover, added unmodified GNCC or PCC may serve as stiffening agent and may have a positive impact on the extrudate if used as packaging material.
- the mixture obtained in step (c) thus comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of unmodified GNCC or PCC, based on the total dry weight of said mixture.
- said unmodified GNCC or PCC is a food-grade GNCC or PCC.
- said unmodified ground natural or precipitated calcium carbonate is in form of particles having a weight median particle size d 50 (wt) of from 0.05 to 10.0 ⁇ m, preferably from 0.2 to 5.0 ⁇ m, more preferably from 0.4 to 3.0 ⁇ m, most preferably from 0.6 to 1.2 ⁇ m, and especially 0.7 ⁇ m.
- the unmodified ground natural or precipitated calcium carbonate is in form of particles having a top cut particle size d 98 (wt) of from 0.15 to 55 ⁇ m, preferably from 1 to 40 ⁇ m, more preferably from 2 to 25 ⁇ m, most preferably from 3 to 15 ⁇ m, and especially 4 ⁇ m.
- the mixture obtained in step (c) may contain added modified starch and/or cellulose, excluding fibrillated cellulose, which may serve, for example, as stabilizer, dispersant, thickener or texture modifier.
- the mixture obtained in step (c) therefore contains added modified starch, preferably in an amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%, based on the total dry weight of said mixture.
- step (c) there exist also two ways for combining the foregoing additives with the mixture of step (c), namely separate feeding to the extruder and pre-mixing.
- the additives are fed separately to the extruder inlet, meaning that the raw mixture of step (c) comprising the polysaccharide-containing ground material, the extrusion aid and further additives is formed within the extruder. Side-feeding of additives may also be applied.
- the polysaccharide-containing ground material provided in step (a), the extrusion aid provided in step (b) and the further additives are pre-mixed to obtain the mixture of step (c) which is then fed to the extruder inlet.
- Suitable mixing methods are the same as described hereinabove.
- a combination of separate feeding and pre-mixing may be used to obtain the mixture of step (c) comprising the polysaccharide-containing ground material, the extrusion aid and further additives.
- step (d) of the process according to the present invention the mixture obtained in step (c) is puffed by means of an extruder to obtain a puffed polysaccharide-based extrudate.
- a puffed material in the meaning of the present invention provides the skeletal construct of a porous or foamy structure obtained through porous expansion of a suitable starting formulation.
- expansion is achieved by evaporation of a liquid (e.g. water) embedded in said starting formulation using elevated temperatures and/or rapid pressure decrease.
- a liquid e.g. water
- an extruder is used to convert the mixture obtained in step (c) into a puffed material.
- any known extruder type may be used.
- the extruder thus may be a single-screw or twin-screw extruder.
- the extruder is a twin-screw extruder, most preferably a co-rotating twin-screw extruder.
- the extruder may have various configurations. According to one embodiment of the present invention, the extruder has a screw diameter ranging from 35 to 55 mm, preferably from 40 to 50 mm, for example 44 mm.
- the extruder is operated at a screw speed of 60 to 450 rpm with co-rotating twin screws having the following screw configuration.
- the symbols "/"and “ ⁇ ” are used to indicate the conveying direction and number of the screw elements: Feeder Mixing Conv. Pressure Temp. Shear Zone Number / Dir. /// / ⁇ / /// /// // // ⁇ / ⁇ /// Gradient [°] 66 44 poly 66 44 33 44 44 44 33 Length [mm] 66 44 20 66 44 33 15 15 15 33 Offset [°] - - - - 0 0 90 90 90 90 90 90 90 90
- the feeder zone consists of 3 elements DNDL 66/R66 and 1 element DNDL 44/R44
- the mixing zone consists of 2 elements of DNDL P45-4/L20
- the conveying zone consists of 1 element of DNDL 66/R66
- the pressure zone consists of 6 elements of DNDL 44/R44e
- the temperature zone consists of 4 elements of DNDL 33/R33
- the shear zone consists of 6 elements: 1 element of DNDL 44/L14.7, 1 element of DNDL 44/R14.7, 1 element of DNDL 44/L14.7 and 3 elements of DNDL 33/L33.
- the characteristics of the extrudate may also be influenced by process parameters, such as moisture, temperature or pressure.
- step (d) is characterized in that the mixture obtained in step (c) is heated to a temperature of from 100°C to 150°C, preferably from 105°C to 140°C, more preferably from 110°C to 135°C, and most preferably from 115°C to 130°C.
- step (d) is characterized in that the extruder operates at a minimum pressure of 0.5 MPa, preferably 2.5 MPa, more preferably 3.5 MPa, even more preferably 5 MPa, even more preferably 5.5 MPa, and most preferably 6 MPa. Additionally or alternatively, the extruder operates at a maximum pressure of 10 MPa, preferably 8 MPa, more preferably 7.5 MPa, even more preferably 6 MPa, and most preferably 5 MPa.
- suitable die forms and die combinations used at the extruder outlet include (hole diameter in parentheses): 2 ⁇ 1-hole die (3.3 mm), 2 ⁇ 1-hole die (5.0 mm), 2 ⁇ 6-hole die (3.0 mm), 2 ⁇ 10-hole die (2.0 mm), 2 ⁇ 12-hole die (1.0 mm), 1 ⁇ 2-hole die (3.0 mm), 1 ⁇ 2-hole die (star shaped), 1 ⁇ 2-hole die (tube, 3.0 and 2.0 mm).
- Preferred die forms and combinations are selected from 2 ⁇ 1-hole die (3.3 mm) and 1 ⁇ 2-hole die (3.0 mm).
- the cross sectional area of the dies may range from 2 to 100 mm 2 , more preferably from 5 to 50 mm 2 , and most preferably from 10 to 20 mm 2 .
- the puffed polysaccharide-based extrudate obtained in step (d) may thus have any conceivable shape (chips, flakes, spheres, cylinders etc.) depending on the extruder configuration (die form, cutting device, torque, blade speed etc.).
- the product obtainable according to the process of the present invention is a puffed polysaccharide-based material excluding fibrillated cellulose-containing materials (i.e. materials containing microfibrillated cellulose, materials containing nanofibrillated cellulose, materials containing nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill), meaning that it is produced from a polysaccharide-containing material excluding those containing fibrillated cellulose.
- fibrillated cellulose-containing materials i.e. materials containing microfibrillated cellulose, materials containing nanofibrillated cellulose, materials containing nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill
- the term puffed indicates that the corresponding starting material has been subjected to an expansion step, preferably achieved by evaporation of a liquid (e.g. water) embedded in said starting material using elevated temperatures and/or rapid pressure decrease. In the present case, extrusion cooking is applied.
- a liquid e.g. water
- the starting material undergoes no or only little chemical conversion during the expansion process so that, according to a preferred embodiment, the puffed polysaccharide-based material obtainable according to the present invention is a puffed polysaccharide-containing material.
- the product obtainable according to the inventive process thus contains at least one polysaccharide (excluding fibrillated cellulose), at least one extrusion aid and, optionally, one or more additives selected from fillers, dispersants, lubricants, leavenings, nucleating agents, colorants, flavorants, and the like.
- the product obtainable according to the inventive process further comprises whole grains, preferably in amount of from 0.1 to 30 wt.-%, more preferably from 0.5 to 20 wt.-%, and most preferably from 1 to 15 wt.-%, based on the total dry weight of said product.
- the product obtainable according to the inventive process further comprises sucrose, preferably in amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%, based on the total dry weight of said product.
- the product obtainable according to the inventive process further comprises sodium chloride, preferably in amount of from 0.001 to 5 wt.-%, more preferably from 0.01 to 2 wt.-%, and most preferably from 0.1 to 1 wt.-%, based on the total dry weight of said product.
- the product obtainable according to the inventive process may also contain unmodified GNCC or PCC.
- the mixture obtained in step (c) thus comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of unmodified GNCC or PCC, based on the total dry weight of said product.
- said unmodified GNCC or PCC is a food-grade GNCC or PCC.
- the puffed polysaccharide-based material according to the present invention provides improved characteristics compared with conventional extrusion cooked puffed materials, such as material prepared without extrusion aid or with unmodified GNCC or PCC.
- the inventive puffed extrusion cooked material provides an increased expansion index which is associated with a lower density.
- the puffed polysaccharide-based material provides an expansion index F of from 5 to 30, preferably from 8 to 25, more preferably from 10 to 20, and most preferably from 12 to 18.
- the puffed polysaccharide-based material provides a crispness of from 25 to 50 N, preferably from 30 to 48 N, more preferably from 32 to 45 N, and most preferably from 35 to 40 N, measured on a TA.HDplus Texture Analyser from Stable Micro Systems equipped with a Kramer Shear cell with 10 blades.
- the inventive process therefore comprises step (e) of processing the puffed polysaccharide-based extrudate obtained in step (d) into:
- Food products for animal consumption further may include food products for farm animals such as cattle, cow, horse, pork, and poultry food.
- Typical processing steps of the foregoing embodiment include deep frying as well as the addition of colorants or flavorants.
- the puffed polysaccharide-based material may also be used as or processed into a packaging material for example in the form of chips, flakes, spheres, cylinders etc.
- the inventive process therefore comprises step (e) of processing the puffed polysaccharide-based extrudate obtained in step (d) into a packaging material.
- the packaging materials according to the present invention may be biodegradable.
- extrusion aid contained in the puffed polysaccharide-based material according to the present invention is a calcium salt and therefore may also serve as a calcium source for dietary purposes.
- volume determined median particle size d 50 (vol) and the volume determined top cut particle size d 98 (vol) were evaluated using a Malvern Mastersizer 2000 Laser Diffraction System (Malvern Instruments Plc., Great Britain). The raw data obtained by the measurement was analysed using the Fraunhofer theory without specified refractive index, with an absorption index of 0.005. The methods and instruments are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments.
- the weight determined median particle size d 50 was measured by the sedimentation method, which is an analysis of sedimentation behaviour in a gravimetric field.
- the measurement was made with a SedigraphTM 5120 of Micromeritics Instrument Corporation, USA. The method and the instrument are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments.
- the measurement was carried out in an aqueous solution of 0.1 wt.-% Na 4 P 2 O 7 .
- the samples were dispersed using a high speed stirrer and sonicated.
- SSA Specific surface area
- the specific surface area was measured via the BET method according to ISO 9277:1995 using nitrogen, following conditioning of the sample by heating at 250°C for a period of 30 minutes. Prior to such measurements, the sample was filtered within a Büchner funnel, rinsed with deionised water and dried overnight at 90 to 100°C in an oven. Subsequently, the dry cake was ground thoroughly in a mortar and the resulting powder was placed in a moisture balance at 130°C until a constant weight was reached.
- the specific pore volume was measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 ⁇ m.
- the equilibration time used at each pressure step was 20 seconds.
- the sample material was sealed in a 5 cm 3 chamber powder penetrometer for analysis.
- the data were corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Comp ( Gane, P.A.C., Kettle, J.P., Matthews, G.P. and Ridgway, C.J., "Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations", Industrial and Engineering Chemistry Research, 35(5), 1996, pp. 1753-1764 ).
- the expansion index F is a measure to describe the cross-sectional expansion of an extrudate after passing the outlet of an extruder.
- Samples are weighed so that equally defined portions are obtained. The amount must be such that at least half of the Kramer shear cell is filled volumetrically.
- the Kramer shear cell simulates a single bite on a sample and thus provides information about bite-behaviour, crispness and consistency.
- the 10 blades are moved with constant velocity through the sample, compressing, shearing and extruding the sample through the slotted base plate. Measuring of multiple blades at the same time results in measuring at different places in the sample (resistance in Newtons) for levelling out local structural differences. Measuring parameters are set out in the table below. T.A.
- the following mineral materials are used as extrusion aids or as corresponding reference materials.
- SRCC1 was obtained by preparing 450 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground marble calcium carbonate from Hustadmarmor, Norway, having a mass based median particle size distribution of 90 % less than 2 ⁇ m, as determined by sedimentation, such that a solids content of 16 wt.-%, based on the total weight of the aqueous suspension, is obtained.
- SRCC2 was obtained by preparing 10 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground limestone calcium carbonate from Omya SAS, Orgon, having a mass based median particle size distribution of 90 % less than 1 ⁇ m, as determined by sedimentation, such that a solids content of 10 wt.-%, based on the total weight of the aqueous suspension, is obtained.
- a calcium carbonate suspension is prepared by adding water and undispersed limestone (ground under wet conditions in water, optionally in the presence of a food approved dispersing or grinding aid such as monopropyleneglycol (MPG)) having a d 50 (wt) of 3 ⁇ m, wherein 33 wt.-% of particles have a diameter of less than 2 ⁇ m in a 20 L stainless steel reactor, such that the aqueous suspension obtained has a solids content corresponding to 16 wt.-% by dry weight relative to the total suspension weight. The temperature of this suspension is thereafter is brought to and maintained at 70°C.
- MPG monopropyleneglycol
- phosphoric acid in the form of a 30 % solution is added to the calcium carbonate suspension through a separate funnel over a period of 10 minutes in an amount corresponding to 30 % by weight on dry calcium carbonate weight. Following this addition, the suspension is stirred for an additional 5 minutes. The resulting suspension was allowed to settle overnight, and the SRCC had a specific surface area of 36 m 2 /g, a d 50 (vol) of 9.3 ⁇ m (Malvern) and d 98 (vol) of 23.5 ⁇ m (Malvern).
- a calcium carbonate suspension is prepared by adding water and undispersed marble (ground under wet conditions in water, optionally in the presence of a food approved dispersing or grinding aid such as monopropyleneglycol (MPG)) having a d 50 (wt) of 3.5 ⁇ m, wherein 33 wt.-% of particles have a diameter of less than 2 ⁇ m in a 20 L stainless steel reactor, such that the aqueous suspension obtained has a solids content corresponding to 16 wt.-% by dry weight relative to the total suspension weight. The temperature of this suspension is thereafter is brought to and maintained at 70°C.
- MPG monopropyleneglycol
- phosphoric acid in the form of a 30 % solution is added to the calcium carbonate suspension through a separate funnel over a period of 10 minutes in an amount corresponding to 30 % by weight on dry calcium carbonate weight. Following this addition, the suspension is stirred for an additional 5 minutes. The resulting suspension was allowed to settle overnight, and the SRCC had a specific surface area of 46 m 2 /g, a d 50 (vol) of 9.5 ⁇ m (Malvern) and d 98 (vol) of 18.9 ⁇ m (Malvern).
- a calcium carbonate suspension is prepared by adding water and undispersed marble of (ground under wet conditions in water, optionally in the presence of a food approved dispersing or grinding aid such as monopropyleneglycol (MPG)) having a d 50 (wt) of 2 ⁇ m in a 20 L stainless steel reactor, such that the aqueous suspension obtained has a solids content corresponding to 16 wt.-% by dry weight relative to the total suspension weight. The temperature of this suspension is thereafter is brought to and maintained at 70°C.
- MPG monopropyleneglycol
- phosphoric acid in the form of a 30% solution is added to the calcium carbonate suspension through a separate funnel over a period of 10 minutes in an amount corresponding to 50% by weight on dry calcium carbonate weight. Following this addition, the suspension is stirred for an additional 5 minutes. The resulting suspension was allowed to settle overnight, and the SRCC had a specific surface area of 71 m 2 /g, a d 50 (vol) of 10.6 ⁇ m (Malvern) and d 98 (vol) of 21.8 ⁇ m (Malvern).
- the feeder zone consisted of 3 elements DNDL 66/R66 and 1 element DNDL 44/R44
- the mixing zone consisted of 2 elements of DNDL P45-4/L20
- the conveying zone consisted of 1 element of DNDL 66/R66
- the pressure zone consisted of 6 elements of DNDL 44/R44e
- the temperature zone consisted of 4 elements of DNDL 33/R33
- the shear zone consisted of 6 elements: 1 element of DNDL 44/L14.7, 1 element of DNDL 44/R14.7, 1 element of DNDL 44/L14.7 and 3 elements of DNDL 33/L33.
- Figures 1 to 5 show the results for the diameter of the extrudate ( Fig. 1 : snacks, Fig. 2 : cereals), the expansion index ( Fig. 3 : snacks, Fig. 4 : cereals), and the crispness of snacks ( Fig. 5 ).
- Figures 6 and 7 show photographs of standard cereals ( Fig. 6 ) and of cereals prepared in the presence of 0.5 % SRCC2 ( Fig. 7 ).
- Figures 8 and 9 show stereo microscope (SM) images of the cross section of a standard snack ( Fig. 8 ) and of a snack that was prepared in the presence of SRCC3 - 0.5 % ( Fig.9 ).
- the images were made with a Leica MZ16A stereo microscope and a Leica DFC 320 camera and angled light illumination to show the structure of the samples.
- Organoleptic panel tests were carried out for the produced snacks as well as for the produced cereals.
- the organoleptic panel consisted of 6 persons, all trained according to DIN 10961.
- Tables 1 and 2 show the results obtained for snacks and cereals, respectively.
- the results of the present examples indicate an increased expansion index ( F ) and improved crispness (TA.HDplus Texture Analyser ) for the products prepared according to the inventive process compared with the samples prepared from standard calcium carbonate (GNCC1) which were prepared analogously (see Figures 1 to 5 ). Furthermore, the organoleptic panel test revealed improved surface textures and crispness (see the foregoing tables).
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Description
- The present application relates to the use of surface-reacted calcium carbonate as extrusion aid for the production of puffed polysaccharide-based materials.
- Puffed polysaccharide-based materials obtained by means of extrusion cooking are very often used as or processed into food products for human consumption (e.g. breakfast cereals or snacks) or for animal consumption (e.g. pet food). However, the use of these polysaccharide-based materials is also common for non-food applications, particularly for packaging materials.
- To obtain a puffy structure with a porous or foamy appearance, such materials are frequently produced from starch-containing ground materials or other polysaccharide-containing ground materials which are then subjected to an extrusion process. Suitable starting materials thus include groat, semolina or flour of barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet and the like. In a typical process, the ground starting material is fed to the inlet of an extruder and then heated to temperatures of 100°C or higher. After leaving the extruder through a die, water and other volatiles contained in the starting material evaporate immediately which is associated with a cross-sectional or volume expansion of the extrudate. Said expansion may be described by the so-called expansion index F, wherein a high expansion index indicates a higher porosity and a lower density of the extrudate.
- The terms "puffy" or "puffed" as used throughout this application refer to the property of a solid material providing the skeletal construct of a porous or foamy structure obtained through porous expansion of a suitable starting formulation. Preferably, expansion is achieved by evaporation of a liquid (e.g. water) embedded in said starting formulation using elevated temperatures and/or rapid pressure decrease.
- In the art, the extrusion of polysaccharide-containing materials for the production of puffed extrusion products is well-established. An overview of suitable methods and raw materials is provided by R. Guy in "Extrusion Cooking", Woodhead Publishing Ltd. and CRC Press LLC, 2001.
- Efforts have been made in order to modify or control the porosity and further characteristics of polysaccharide-based food products.
US 6,277,423 suggests the use of calcium carbonate as leavening in extruded dough compositions. However, the leavening described therein was given to have a larger particle size to prevent it from evolving gas before frying the extrudate.US 7,431,954 discloses the use of calcium carbonate to provide calcium fortification in extrusion cooked food products. However, it is described that calcium carbonate may cause over leavening which can actually result in unwanted under-expansion of the extrudate. -
US2009/0291179 A1 andUS2012/0064209 A1 disclose methods for manufacturing extruded snack products, using calcium carbonate as an expansion controlling agent. Accordingly, there is still a need for the provision of improved extrusion cooked puffed materials and improved processes for their production. - One object of the present invention may therefore be seen in the provision of puffed extrusion cooked materials with an increased expansion index. In this respect, there is still a need for the provision of food products with a lighter and fluffier mouthfeel. Especially also in the field of packing materials, there is still a need for lighter and environmentally friendly packaging materials.
- Another object may be seen in the provision of puffed extrusion cooked food products with improved crispness.
- Still another object may be seen in the provision of a puffed extrudate having a smoother or more uniform texture.
- Still another object may be seen in the provision of a puffed extrudate with increased hardness. In case of puffed food, increased hardness may positively affect the mouthfeel. In the field of packaging materials, increased hardness is associated with improved stability and safety of transported goods.
- Still another object may be seen in the provision of a material and cost saving process for the production of puffed polysaccharide-based materials.
- The foregoing and other problems may be solved by the subject-matter as defined herein in the independent claims.
- A first aspect of the present invention relates to a process for the production of a puffed polysaccharide-based material, the process comprising the following steps:
- (a) providing at least one polysaccharide-containing ground material excluding fibrillated cellulose-containing materials;
- (b) providing at least one extrusion aid;
- (c) combining the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) to obtain a mixture; and
- (d) puffing the mixture obtained in step (c) by means of an extruder to obtain a puffed polysaccharide-based extrudate;
- The use of (unmodified) calcium carbonate as additive in extruded or puffed cereal-based snacks is already known. However, most of the described food products contain calcium salts for fortification purposes.
US 6,210,741 discloses a method for preparing a grain-based extrudate wherein the starting blend can comprise about 1 to 10% of calcium fortification (e.g., calcium carbonate or calcium phosphate). In a similar manner,US 5,366,748 discloses a method for the production of cereal grain-based food products, wherein calcium carbonate was added as a calcium fortification source. - The inventors of the present invention surprisingly found that the use of surface-reacted calcium carbonate as extrusion additive provides improved characteristics to puffed polysaccharide-based materials obtained by means of extrusion. For this purpose, a mixture comprising a suitable puffable material and surface-reacted calcium carbonate are subjected to an extrusion step, i.e. at elevated temperatures and elevated pressure. Suitable puffable materials may be, for example, groat, semolina or flour of barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet and the like excluding fibrillated cellulose-containing materials (i.e. materials containing microfibrillated cellulose, materials containing nanofibrillated cellulose, materials containing nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill). The surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC) treated with CO2 and one or more H3O+ ion donors. While not wishing to be bound by any theory, it is believed that the surface-reacted calcium carbonate serves as a so-called "bubble nucleating agent" which provides large surfaces and enhances or accelerates the evaporation of liquids, such as water, contained in the raw mixture at the outlet of the extruder.
- Improved characteristics of the puffed extrudate obtainable by means of the inventive process include increased expansion indices, which may be used to describe the cross-sectional or volume expansion of the extrudate after passing the outlet of an extruder. Further to this, the products obtainable according to the inventive extrusion process were found to provide improved results in organoleptic panel testing, for example improved crispness or a more uniform surface.
- Another aspect of the present invention relates to the use of a surface-reacted calcium carbonate as extrusion aid for the production of a puffed polysaccharide-based material excluding fibrillated cellulose-containing materials, wherein the surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC) treated with CO2 and one or more H3O+ ion donors and wherein the CO2 is formed in situ by the H3O+ ion donors treatment and/or is supplied from an external source.
- Still another aspect of the present invention relates to a puffed polysaccharide-based material excluding fibrillated cellulose-containing materials, obtainable according to the inventive process.
- The following terms used throughout the present application shall have the meanings set forth hereinafter:
The term "solid" refers to a physical state of a material. Unless indicated otherwise, this physical state is to be observed at a temperature of 20°C. - The term "surface-reacted" (e.g. surface-reacted GNCC or PCC) in the meaning of the present application shall be used to indicate that a material has been subjected to a process comprising partial dissolution of said material upon acidic treatment (e.g., by use of water soluble free acids and/or acid salts) in an aqueous environment followed by a crystallization process which may occur in the absence or presence of further crystallization additives. The term "acid" as used herein refers to an acid in the meaning of the definition by Bronsted and Lowry (e.g. H2SO4, HSO4 -).
- Additionally or alternatively, a "surface-reacted" material may be characterized by an increased intraparticle intruded specific pore volume as compared to the untreated starting material (i.e. GNCC or PCC). Said increased pore volume or porosity is a result of the dissolution and recrystallisation process during its formation. Usually, the starting materials do not show any or only low internal porosity.
- Where an indefinite or definite article is used when referring to a singular noun, e.g. "a", "an" or "the", this includes a plural of that noun unless anything else is specifically stated.
- Where the term "comprising" is used in the present description and claims, it does not exclude other elements. For the purposes of the present invention, the term "consisting of' is considered to be a preferred embodiment of the term "comprising". If hereinafter a group is defined to comprise at least a certain number of embodiments, this is also to be understood to disclose a group, which preferably consists only of these embodiments.
- Terms like "obtainable" or "definable" and "obtained" or "defined" are used interchangeably. This, for example, means that, unless the context clearly dictates otherwise, the term "obtained" does not mean to indicate that, for example, an embodiment must be obtained by, for example, the sequence of steps following the term "obtained" though such a limited understanding is always included by the terms "obtained" or "defined" as a preferred embodiment.
- Whenever the terms "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined hereinabove.
- Further definitions of terms and parameters referred to in the present applications can be found in the experimental section together with, as far as necessary, the measuring methods.
- Advantageous embodiments of the inventive extrusion process, the use of surface-reacted calcium carbonate in said process and the corresponding product are defined in the corresponding subclaims.
- According to one embodiment of the present invention, (i) the polysaccharide is a homopolysaccharide and preferably is starch; and/or (ii) the polysaccharide-containing ground material provided in step (a) comprises barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof, preferably the polysaccharide-containing ground material is selected from groat, semolina or flour of barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof, and more preferably the polysaccharide-containing ground material is corn (maize) flour, wheat flour, nut flour or a mixture thereof.
- According to another embodiment of the present invention, the one or more H3O+ ion donors are selected from (i) strong acids having a pKa of 0 or less at 20°C; and/or (ii) medium-strong acids having a pKa value from 0 to 2.5 at 20°C; and/or (iii) weak acids having a pKa of greater than 2.5 and less than or equal to 7 at 20°C, associated with the ionisation of its first available hydrogen, wherein a corresponding anion is formed on loss of this first available hydrogen capable of forming a water-soluble calcium salt, and wherein at least one water-soluble salt, which in the case of a hydrogen-containing salt has a pKa of greater than 7 at 20°C, associated with the ionisation of the first available hydrogen, and the salt anion of which is capable of forming water-insoluble calcium salts, is additionally provided.
- According to still another embodiment of the present invention, the surface-reacted calcium carbonate is obtained by a process comprising the following steps:
- (a) providing a suspension of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC);
- (b) adding at least one acid having a pKa value of 0 or less at 20°C, or having a pKa value from 0 to 2.5 at 20°C to the suspension provided in step (a); and
- (c) treating the suspension provided in step (a) with CO2 before, during or after step (b).
- According to another embodiment of the present invention, the surface-reacted calcium carbonate is obtained by a process comprising the following steps:
- (a) providing ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC);
- (b) providing at least one water-soluble acid;
- (c) providing gaseous CO2; and
- (d) contacting said GNCC or PCC provided in step (a), the at least one acid provided in step (b) and the gaseous CO2 provided in step (c);
- According to still another embodiment of the present invention, (i) the natural calcium carbonate is selected from the group consisting of marble, chalk, dolomite, limestone and mixtures thereof; and/or (ii) the precipitated calcium carbonate comprises aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof.
- According to another embodiment of the present invention, the extrusion aid has (i) a volume median grain diameter d 50(vol) of from 1 to 75 µm, preferably from 1.5 to 50 µm, more preferably from 2 to 40 µm, and most preferably from 2.5 to 7.0 µm; and/or (ii) a volume grain diameter d 98(vol) of from 2 to 150 µm, preferably from 4 to 100 µm, more preferably from 6 to 80 µm, even more preferably from 8 to 60 µm, and most preferably from 10 to 30 µm.
- According to another embodiment of the present invention, the extrusion aid has a specific surface area of from 15 to 200 m2/g, preferably from 27 to 180 m2/g, more preferably from 30 to 160 m2/g, even more preferably from 45 to 150 m2/g, and most preferably from 48 to 140 m2/g, measured using nitrogen and the BET method according to ISO 9277:1995.
- According to another embodiment of the present invention, the mixture obtained in step (c) comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of the extrusion aid provided in step (b), based on the total dry weight of said mixture.
- According to another embodiment of the present invention, (i) the mixture obtained in step (c) is heated to from 100°C to 150°C, preferably from 105°C to 140°C, more preferably from 110°C to 135°C, and most preferably from 115°C to 130°C; and/or (ii) the extruder operates at a minimum pressure of 0.5 MPa, preferably 2.5 MPa, more preferably 3.5 MPa, even more preferably 5 MPa, even more preferably 5.5 MPa, and most preferably 6 MPa; and/or (iii) the extruder operates at a maximum pressure of 10 MPa, preferably 8 MPa, more preferably 7.5 MPa, even more preferably 6 MPa, and most preferably 5 MPa.
- According to still another embodiment of the present invention, the mixture obtained in step (c) further comprises the following additives: (i) water, preferably in amount of from 0.01 to 15 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%; and/or (ii) whole grains, preferably in amount of from 0.1 to 30 wt.-%, more preferably from 0.5 to 20 wt.-%, and most preferably from 1 to 15 wt.-%; and/or (iii) sucrose, preferably in amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%; and/or (iv) sodium chloride, preferably in amount of from 0.001 to 5 wt.-%, more preferably from 0.01 to 2 wt.-%, and most preferably from 0.1 to 1 wt.-%; each based on the total dry weight of said mixture.
- According to still another embodiment of the present invention, the process further comprises step (e) of processing the puffed polysaccharide-based extrudate obtained in step (d) into: (i) a food product for human consumption, preferably breakfast cereals and/or snacks; or (ii) a food product for animal consumption, preferably pet food, and more preferably fish food, bird food, dog food and/or cat food; or (iii) a packaging material.
- According to still another embodiment of the present invention, the puffed polysaccharide-based material obtainable according to the inventive process provides: (i) an expansion index F of from 5 to 30, preferably from 8 to 25, more preferably from 10 to 20, and most preferably from 12 to 18; and/or (ii) a crispness of from 25 to 50 N, preferably from 30 to 48 N, more preferably from 32 to 45 N, and most preferably from 35 to 40 N, measured on a TA.HDplus Texture Analyser from Stable Micro Systems equipped with a Kramer Shear cell with 10 blades.
- In the following, embodiments of the inventive extrusion process using surface-reacted calcium carbonate will be described in detail. It is to be understood that these details and embodiments also apply to the use of the surface-reacted calcium carbonate for the purpose of the present invention. Where appropriate, these details further apply to the product obtainable according to the inventive process.
- The base material used in the extrusion process according to the present invention is a polysaccharide-containing ground material, excluding fibrillated cellulose-containing materials (i.e. materials containing microfibrillated cellulose, materials containing nanofibrillated cellulose, materials containing nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill), and is provided in step (a).
- A "polysaccharide" in the meaning of the present invention is understood to be a polymeric carbohydrate composed of long chains of monosaccharide units, preferably 10 or more units, bound together by glycosidic linkages, excluding fibrillated cellulose. Typical examples of polysaccharides include glycogen, starch, pectines, chitin, callose, or cellulose excluding fibrillated cellulose.
- Accordingly, the term "polysaccharide" shall not include fibrillated cellulose in any of the aspects and embodiments disclosed in the present application. The expression "fibrillated cellulose" as used herein is a collective referring to both micro- and nanofibrillated cellulose, nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill.
- When fibres are refined under high energy, they become fibrillated as the cell walls are broken and torn into attached strips, i.e. into fibrils. If this process is continued to separate the fibrils from the body of the fibre, it releases said fibrils. The breakdown of fibres into isolated microfibrils is referred to as "microfibrillation". This process may be continued until there are no fibres left and only elementary or primary fibrils remain which have a nanosized diameter. The foregoing breakdown of fibres into isolated elementary or primary fibrils is referred to as "nanofibrillation".
- The corresponding celluloses are referred to as microfibrillated cellulose and nanofibrillated cellulose, respectively. Accordingly, the term "microfibrillated cellulose" in the context of the present invention relates to a plurality of fibres, which is at least partially broken down to microfibrils, preferably microfibrillated cellulose is essentially free or free of isolated primary or elementary fibrils. In a similar manner, the term "nanofibrillated cellulose" relates to a plurality of fibres, which is at least partially broken down to primary or elementary fibrils, preferably nanofibrillated cellulose is essentially free or free of isolated microfibrils. In the meaning of the present application, a material is "essentially" free of a specific substance if the amount of that substance may vary within a certain tolerable range without deviating from the basic concept underlying the present invention. Preferably, a material is "essentially" free of a specific substance if it contains less than 10 wt.-% of that substance, more preferably less than 5 wt.-% and most preferably less than 1 wt.-%, based on the total dry weight of said material.
- In one embodiment, the polysaccharide is a homopolysaccharide meaning that the polysaccharide is composed of a plurality of identical monosaccharide units. In such case, the product obtained according to the present invention is a puffed homopolysaccharide-based material. Preferably, the monosaccharide is selected from glucose and/or fructose. Examples of suitable glucose or fructose homopolysaccharides thus include starch, glycogen, callose, cellulose excluding fibrillated cellulose, and inulin.
- A particularly preferred (homo-)polysaccharide is starch. Starch is a homopolymer of glucose and is used as a storage polysaccharide in plants, being found in the form of both amylose and the branched amylopectin. In the meaning of the present application, the term "starch" refers to a mixture of amylose and amylopectin unless indicated otherwise.
- Suitable polysaccharide-containing materials are cereals. In one embodiment, the polysaccharide-containing ground material therefore is a ground cereal. In a preferred embodiment, said cereal is selected from barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof. If cereals are used as the polysaccharide-containing material, it is in principle possible to use both ground whole grains and ground refined grains to provide the polysaccharide-containing ground material of step (a). In one embodiment, the polysaccharide-containing ground material is therefore selected from ground whole grain cereals or ground refined grain cereals. In a preferred embodiment, the polysaccharide-containing ground material is a ground refined grain cereal.
- The product obtainable according to the inventive process is a puffed material, meaning that it has an expanded porous or foamy structure which is caused by evaporation of a liquid (e.g. water) embedded in the polysaccharide-containing starting material by applying elevated temperatures and/or rapid pressure decrease. For the purpose of the present invention, at least part of the starting material provided in step (a) is a ground material in order to ensure that the extrusion aid is in contact with the polysaccharide.
- The ground material provided in step (a) may in principle have any grinding degree, i.e. it may be finely ground or coarsely ground. According to one embodiment, the polysaccharide-containing ground material is provided in the form of groat, semolina or flour. According to another embodiment, the polysaccharide-containing ground material is provided in the form of flour. Therefore, a preferred embodiment of the inventive process uses cereal flour as the polysaccharide-containing ground material.
- Additionally, also non-cereal flours from other polysaccharide sources may be used such as, for example, potato flour, tapioca flour, nut-flour or mixtures thereof. Examples of nut flour are almond, coconut, hazelnut, pecan, and macadamia flour or mixtures thereof.
- According to another preferred embodiment, the polysaccharide-containing ground material is selected from groat, semolina or flour of the following suitable cereals: barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof. More preferably, the polysaccharide-containing ground material is corn (maize) flour, wheat flour, nut flour or a mixture thereof.
- In some embodiments of the present invention, it may be sufficient if at least part of the starting material in step (a) is provided as a ground material. Therefore, it is also possible to use a mixture of ground materials, for example any of the flours described hereinabove, and whole grains.
- The polysaccharide-containing ground material provided in step (a) may contain water or other evaporable liquids. In case of using ground cereals or other starch-containing ground materials, the polysaccharide-containing ground material naturally contains water. In some embodiments, the polysaccharide-containing ground material provided in step (a) contains water in an amount of from 0.05 to 50 wt.-%, preferably from 0.1 to 40 wt.-%, more preferably from 0.5 to 30 wt.-%, and most preferably from 1 to 25 wt.-%, based on the total weight of the polysaccharide-containing ground material.
- The extrusion aid defined in step (b) of the inventive process is a surface-reacted calcium carbonate (SRCC). Surface-reacted calcium carbonate is also referred to as functionalized calcium carbonate (FCC).
- The surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate or precipitated calcium carbonate treated with CO2 and one or more H3O+ ion donors, wherein the CO2 is formed in situ by the H3O+ ion donors treatment and/or is supplied from an external source.
- An H3O+ ion donor in the context of the present invention is a Bronsted acid and/or an acid salt.
- In a preferred embodiment of the invention, the surface-reacted calcium carbonate is obtained by a process comprising the steps of:
- (a) providing a suspension of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC);
- (b) adding at least one acid having a pKa value of 0 or less at 20°C, or having a pKa value from 0 to 2.5 at 20°C to the suspension provided in step (a); and
- (c) treating the suspension provided in step (a) with CO2 before, during or after step (b).
- According to another embodiment, the surface-reacted calcium carbonate is obtained by a process comprising the steps of:
- (a) providing a ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC);
- (b) providing at least one water-soluble acid;
- (c) providing gaseous CO2; and
- (d) contacting said GNCC or PCC provided in step (a), the at least one acid provided in step (b) and the gaseous CO2 provided in step (c);
- The source of calcium carbonate, e.g. "ground natural calcium carbonate" (GNCC), preferably is selected from calcium carbonate-containing minerals selected from the group comprising marble, chalk, limestone and mixtures thereof. Natural calcium carbonate may comprise further naturally occurring components such as magnesium carbonate, alumino silicate etc.
- In general, the grinding of ground natural calcium carbonate may be performed in a dry or wet grinding process and may be carried out with any conventional grinding device, for example, under conditions such that comminution predominantly results from impacts with a secondary body, i.e. in one or more of: a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled person. In case the ground natural calcium carbonate comprises wet ground calcium carbonate, the grinding step may be performed under conditions such that autogenous grinding takes place and/or by horizontal ball milling, and/or other such processes known to the skilled person. The wet processed ground natural calcium carbonate thus obtained may be washed and dewatered by well-known processes, e.g. by flocculation, filtration or forced evaporation prior to drying. The subsequent step of drying (if necessary) may be carried out in a single step such as spray drying, or in at least two steps. It is also common that such a mineral material undergoes a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities.
- A "precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthesized material, generally obtained by precipitation following a reaction of CO2 and calcium hydroxide in an aqueous environment or by precipitation of calcium and carbonate ions, for example CaCl2 and Na2CO3, out of solution. Further possible ways of producing PCC are the lime soda process, or the Solvay process in which PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and vaterite, and there are many different polymorphs (crystal habits) for each of these crystalline forms. Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC). Aragonite is an orthorhombic structure with typical crystal habits of twinned hexagonal prismatic crystals, as well as a diverse assortment of thin elongated prismatic, curved bladed, steep pyramidal, chisel shaped crystals, branching tree, and coral or worm-like form. Vaterite belongs to the hexagonal crystal system. The obtained PCC slurry can be mechanically dewatered and dried.
- According to one embodiment of the present invention, the precipitated calcium carbonate is precipitated calcium carbonate, preferably comprising aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof.
- Precipitated calcium carbonate may be ground prior to the treatment with CO2 and at least one H3O+ ion donor by the same means as used for grinding natural calcium carbonate and described above.
- According to one embodiment of the present invention, the natural or precipitated calcium carbonate is in form of particles having a weight median particle size dso(wt) of from 0.05 to 10.0 µm, preferably from 0.2 to 5.0 µm, more preferably from 0.4 to 3.0 µm, most preferably from 0.6 to 1.2 µm, and especially 0.7 µm. According to a further embodiment of the present invention, the natural or precipitated calcium carbonate is in form of particles having a top cut particle size d 98(wt) of from 0.15 to 55 µm, preferably from 1 to 40 µm, more preferably from 2 to 25 µm, most preferably from 3 to 15 µm, and especially 4 µm.
- The value dx represents the diameter relative to which x % of the particles have diameters less than dx. This means that the d 98 value is the particle size at which 98% of all particles are smaller. The d 98 value is also designated as "top cut". The dx values may be given in volume or weight percent. The d 50(wt) value is thus the "weight median particle size", i.e. 50 wt.-% of all grains are smaller than this particle size, and the d 50(vol) value is the "volume median particle size", i.e. 50 vol.-% of all grains are smaller than this particle size.
- The natural and/or precipitated calcium carbonate may be used dry or suspended in water. Preferably, a corresponding slurry has a content of natural or precipitated calcium carbonate within the range of from 1 to 90 wt.-%, more preferably from 3 to 60 wt.-%, even more preferably from 5 to 40 wt.-%, and most preferably from 10 to 25 wt.-%, based on the total weight of the slurry.
- The one or more H3O+ ion donor used for the preparation of surface reacted calcium carbonate may be any strong acid, medium-strong acid, or weak acid, or mixtures thereof, generating H3O+ ions under the preparation conditions. According to the present invention, the at least one H3O+ ion donor can also be an acid salt, generating H3O+ ions under the preparation conditions.
- According to one embodiment, the at least one H3O+ ion donor is a strong acid having a pKa of 0 or less at 20°C.
- According to another embodiment, the at least one H3O+ ion donor is a medium-strong acid having a pKa value from 0 to 2.5 at 20°C. If the pKa at 20°C is 0 or less, the acid is preferably selected from sulphuric acid, hydrochloric acid, or mixtures thereof. If the pKa at 20°C is from 0 to 2.5, the H3O+ ion donor is preferably selected from H2SO3, H3PO4, oxalic acid, or mixtures thereof. The at least one H3O+ ion donor can also be an acid salt, for example, HSO4 - or H2PO4 -, being at least partially neutralized by a corresponding cation such as Li+, Na+ or K+, or HPO4 2-, being at least partially neutralised by a corresponding cation such as Li+, Na+ ' K+, Mg2+ or Ca2+. The at least one H3O+ ion donor can also be a mixture of one or more acids and one or more acid salts.
- According to still another embodiment, the at least one H3O+ ion donor is a weak acid having a pKa value of greater than 2.5 and less than or equal to 7, when measured at 20°C, associated with the ionisation of the first available hydrogen, and having a corresponding anion, which is capable of forming water-soluble calcium salts. Subsequently, at least one water-soluble salt, which in the case of a hydrogen-containing salt has a pKa of greater than 7, when measured at 20°C, associated with the ionisation of the first available hydrogen, and the salt anion of which is capable of forming water-insoluble calcium salts, is additionally provided. According to a more preferred embodiment, the weak acid has a pKa value from greater than 2.5 to 5 at 20°C, and more preferably the weak acid is selected from the group consisting of acetic acid, formic acid, propanoic acid, and mixtures thereof. Exemplary cations of said water-soluble salt are selected from the group consisting of potassium, sodium, lithium and mixtures thereof. In a more preferred embodiment, said cation is sodium or potassium. Exemplary anions of said water-soluble salt are selected from the group consisting of phosphate, dihydrogen phosphate, monohydrogen phosphate, oxalate, silicate, mixtures thereof and hydrates thereof. In a more preferred embodiment, said anion is selected from the group consisting of phosphate, dihydrogen phosphate, monohydrogen phosphate, mixtures thereof and hydrates thereof. In a most preferred embodiment, said anion is selected from the group consisting of dihydrogen phosphate, monohydrogen phosphate, mixtures thereof and hydrates thereof. Water-soluble salt addition may be performed dropwise or in one step. In the case of drop wise addition, this addition preferably takes place within a time period of 10 minutes. It is more preferred to add said salt in one step.
- According to one embodiment of the present invention, the at least one H3O+ ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid, and mixtures thereof. Preferably the at least one H3O+ ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, H2PO4 -, being at least partially neutralised by a corresponding cation such as Li+, Na+ or K+, HPO4 2-, being at least partially neutralised by a corresponding cation such as Li+, Na+ ' K+, Mg2+, or Ca2+ and mixtures thereof, more preferably the at least one acid is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, or mixtures thereof, and most preferably, the at least one H3O+ ion donor is phosphoric acid.
- The one or more H3O+ ion donor can be added to the suspension as a concentrated solution or a more diluted solution. Preferably, the molar ratio of the H3O+ ion donor to the natural or precipitated calcium carbonate is from 0.01 to 4, more preferably from 0.02 to 2, even more preferably from 0.05 to 1 and most preferably from 0.1 to 0.58.
- As an alternative, it is also possible to add the H3O+ ion donor to the water before the natural or precipitated calcium carbonate is suspended.
- In a next step, the natural or precipitated calcium carbonate is treated with CO2. If a strong acid such as sulphuric acid or hydrochloric acid is used for the H3O+ ion donor treatment of the natural or precipitated calcium carbonate, the CO2 is automatically formed. Alternatively or additionally, the CO2 can be supplied from an external source.
- H3O+ ion donor treatment and treatment with CO2 can be carried out simultaneously which is the case when a strong or medium-strong acid is used. It is also possible to carry out H3O+ ion donor treatment first, e.g. with a medium strong acid having a pKa in the range of 0 to 2.5 at 20°C, wherein CO2 is formed in situ, and thus, the CO2 treatment will automatically be carried out simultaneously with the H3O+ ion donor treatment, followed by the additional treatment with CO2 supplied from an external source.
- Preferably, the concentration of gaseous CO2 in the suspension is, in terms of volume, such that the ratio (volume of suspension):(volume of gaseous CO2) is from 1:0.05 to 1:20, even more preferably 1:0.05 to 1:5.
- In a preferred embodiment, the H3O+ ion donor treatment step and/or the CO2 treatment step are repeated at least once, more preferably several times. According to one embodiment, the at least one H3O+ ion donor is added over a time period of at least about 5 min, preferably at least about 10 min, typically from about 10 to about 20 min, more preferably about 30 min, even more preferably about 45 min, and sometimes about 1 h or more.
- Subsequent to the H3O+ ion donor treatment and CO2 treatment, the pH of the aqueous suspension, measured at 20°C, naturally reaches a value of greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5, thereby preparing the surface-reacted natural or precipitated calcium carbonate as an aqueous suspension having a pH of greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5.
- Further details about the preparation of the surface-reacted natural calcium carbonate are disclosed in
WO 00/39222 A1 WO 2004/083316 A1 ,WO 2005/121257 A2 ,WO 2009/074492 A1 ,EP 2 264 108 A1EP 2 264 109 A1
US 2004/0020410 A1 , the content of these references herewith being included in the present application. - Similarly, surface-reacted precipitated calcium carbonate may be obtained. As can be taken in detail from
WO 2009/074492 A1 , surface-reacted precipitated calcium carbonate is obtained by contacting precipitated calcium carbonate with H3O+ ions and with anions being solubilized in an aqueous medium and being capable of forming water-insoluble calcium salts, in an aqueous medium to form a slurry of surface-reacted precipitated calcium carbonate, wherein said surface-reacted precipitated calcium carbonate comprises an insoluble, at least partially crystalline calcium salt of said anion formed on the surface of at least part of the precipitated calcium carbonate. - Said solubilized calcium ions correspond to an excess of solubilized calcium ions relative to the solubilized calcium ions naturally generated on dissolution of precipitated calcium carbonate by H3O+ ions, where said H3O+ ions are provided solely in the form of a counter ion to the anion, i.e. via the addition of the anion in the form of an acid or non-calcium acid salt, and in absence of any further calcium ion or calcium ion generating source.
- Said excess solubilized calcium ions are preferably provided by the addition of a soluble neutral or acid calcium salt, or by the addition of an acid or a neutral or acid non-calcium salt which generates a soluble neutral or acid calcium salt in situ.
- Said H3O+ ions may be provided by the addition of an acid or an acid salt of said anion, or the addition of an acid or an acid salt which simultaneously serves to provide all or part of said excess solubilized calcium ions.
- In a further preferred embodiment of the preparation of the surface-reacted natural or precipitated calcium carbonate, the natural or precipitated calcium carbonate is reacted with the acid and/or the CO2 in the presence of at least one compound selected from the group consisting of silicate, silica, aluminium hydroxide, earth alkali aluminate such as sodium or potassium aluminate, magnesium oxide, aluminium sulfate or mixtures thereof. Preferably, the at least one silicate is selected from an aluminium silicate, a calcium silicate, or an earth alkali metal silicate. These components can be added to an aqueous suspension comprising the natural or precipitated calcium carbonate before adding the acid and/or CO2.
- Alternatively, the silicate and/or silica and/or aluminium hydroxide and/or earth alkali aluminate and/or magnesium oxide component(s) can be added to the aqueous suspension of natural or precipitated calcium carbonate while the reaction of natural or precipitated calcium carbonate with an acid and CO2 has already started. Further details about the preparation of the surface-reacted natural or precipitated calcium carbonate in the presence of at least one silicate and/or silica and/or aluminium hydroxide and/or earth alkali aluminate component(s) are disclosed in
WO 2004/083316 A1 , the content of this reference herewith being included in the present application. - The surface-reacted calcium carbonate can be kept in suspension, optionally further stabilised by a dispersant. Conventional dispersants known to the skilled person can be used. A preferred dispersant is comprised of polyacrylic acids and/or carboxymethylcelluloses.
- Alternatively, the aqueous suspension described above can be dried, thereby obtaining the solid (i.e. dry or containing as little water that it is not in a fluid form) surface-reacted natural or precipitated calcium carbonate in the form of granules or a powder.
- The surface reacted calcium carbonate may have different particle shapes, such as, for example, the shape of roses, golf balls and/or brains.
- In a preferred embodiment, the extrusion aid has a specific surface area of from 15 to 200 m2/g, preferably from 27 to 180 m2/g, more preferably from 30 to 160 m2/g, even more preferably from 45 to 150 m2/g, and most preferably from 48 to 140 m2/g, measured using nitrogen and the BET method according to ISO 9277:1995. In a further embodiment, the extrusion aid has a specific surface area of 120 m2/g or less, more preferably from 60 to 120 m2/g, and most preferably from 70 to 105 m2/g, measured using nitrogen and the BET method according to ISO 9277:1995. For example, the extrusion aid may have a specific surface area of from 75 to 100 m2/g, measured using nitrogen and the BET method according to ISO 9277:1995.
- It is furthermore preferred that the extrusion aid has a volume median grain diameter d 50(vol) of from 1 to 75 µm, preferably from 2 to 50 µm, more preferably from 3 to 40 µm, even more preferably from 4 to 30 µm, and most preferably from 5 to 15 µm. According to another preferred embodiment, the extrusion aid has a volume median grain diameter d 50(vol) of from 1.5 to 12 µm, preferably from 2 to 5 µm or from 6 to 10 µm.
- It may furthermore be preferred that the extrusion aid has a grain diameter d 98(vol) of from 2 to 150 µm, preferably from 4 to 100 µm, more preferably from 6 to 80 µm, even more preferably from 8 to 60 µm, and most preferably from 10 to 30 µm. According to another preferred embodiment, the extrusion aid has a volume grain diameter d 98(vol) of from 5 to 20 µm, preferably from 8 to 12 µm or from 13 to 18 µm.
- According to a particularly preferred embodiment, the extrusion aid is thus a surface-reacted ground natural calcium carbonate (GNCC) having: (i) a volume median grain diameter dso(vol) of from 1.5 to 12 µm, preferably from 2 to 5 µm or from 6 to 10 µm; and/or (ii) a volume grain diameter d 98(vol) of from 5 to 20 µm, preferably from 8 to 12 µm or from 13 to 18 µm. According to another particularly preferred embodiment, the extrusion aid is a surface-reacted ground natural calcium carbonate (GNCC) having: (i) a volume median grain diameter d 50(vol) of from 1.5 to 12 µm, preferably from 2 to 5 µm or from 6 to 10 µm; and/or (ii) a volume grain diameter d 98(vol) of from 5 to 20 µm, preferably from 8 to 12 µm or from 13 to 18 µm; and/or (iii) a specific surface area of 120 m2/g or less, more preferably from 60 to 120 m2/g, and most preferably from 70 to 105 m2/g, measured using nitrogen and the BET method according to ISO 9277:1995. In the foregoing embodiments, it may further be preferred that the polysaccharide-containing ground material is selected from groat, semolina or flour of the following suitable cereals: barley, corn (maize), oats, rice, rye, spelt and wheat, preferably corn (maize) flour or wheat flour.
- The processes and instruments used to determine the grain size of fillers and pigments are commonly known to the skilled person and are described in more detail in the experimental section.
- According to another preferred embodiment, the extrusion aid has an intra-particle intruded specific pore volume in the range from 0.1 to 2.3 cm3/g, more preferably from 0.2 to 2.0 cm3/g, especially preferably from 0.4 to 1.8 cm3/g and most preferably from 0.6 to 1.6 cm3/g, calculated from mercury porosimetry measurement.
- The intra-particle pore size of the extrusion aid preferably is in a range of from 0.004 to 1.6 µm, more preferably in a range of between 0.005 to 1.3 µm, especially preferably from 0.006 to 1.15 µm and most preferably of 0.007 to 1.0 µm, e.g. 0.004 to 0.50 µm determined by mercury porosimetry measurement.
- The specific pore volume can be measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter.
- The total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 214 µm down to about 1 to 4 µm showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine interparticle packing of the particles themselves. If they also have intraparticle pores, then this region appears bimodal, and by taking the specific pore volume intruded by mercury into pores finer than the modal turning point, i.e. finer than the bimodal point of inflection, we thus define the specific intraparticle pore volume. The sum of these three regions gives the total overall pore volume of the powder, but depends strongly on the original sample compaction/settling of the powder at the coarse pore end of the distribution.
- By taking the first derivative of the cumulative intrusion curve the pore size distributions based on equivalent Laplace diameter, inevitably including pore-shielding, are revealed. The differential curves clearly show the coarse agglomerate pore structure region, the interparticle pore region and the intraparticle pore region, if present. Knowing the intraparticle pore diameter range it is possible to subtract the remainder interparticle and interagglomerate pore volume from the total pore volume to deliver the desired pore volume of the internal pores alone in terms of the pore volume per unit mass (specific pore volume). The same principle of subtraction, of course, applies for isolating any of the other pore size regions of interest.
- In step (c) of the process according to the present invention, the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) are combined to obtain an extrudable mixture. As noted above, according to the present invention the polysaccharide-containing ground material provided in step (a) excludes fibrillated cellulose-containing materials.
- In principle, there exist two ways for preparing the mixture of step (c), namely separate feeding to the extruder and pre-mixing.
- According to a first embodiment, the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) are fed separately to the extruder inlet, meaning that the raw mixture of step (c) comprising the polysaccharide-containing ground material and the extrusion aid is formed within the extruder.
- According to a preferred embodiment, the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) are pre-mixed to obtain the mixture of step (c) which is then fed to the extruder inlet. For this purpose, any suitable mixing device known in the art may be used, for example a spiral kneader or a ploughshare mixer.
- According to still another embodiment, a combination of separate feeding and pre-mixing may be used to obtain the mixture of step (c) comprising the polysaccharide-containing ground material and the extrusion aid.
- In a typical process according to the present invention, the major component of the mixture obtained in step (c), on a dry weights basis, is the polysaccharide-containing ground material. In one embodiment, the mixture obtained in step (c) comprises at least 70 wt.-%, preferably at least 80 wt.-%, and most preferably at least 85 wt.-% of polysaccharide-containing ground material, based on the total dry weight of said mixture. According to another embodiment, the mixture obtained in step (c) comprises from 60 to 99.5 wt.-%, more preferably from 70 to 98.5 wt.-%, and most preferably from 75 to 98 wt.-% of polysaccharide-containing ground material, based on the total dry weight of said mixture.
- The second important component in the raw mixture of step (c) is the extrusion aid which is a surface-reacted calcium carbonate. According to one embodiment of the present invention, the mixture obtained in step (c) comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of said extrusion aid provided in step (b), based on the total dry weight of said mixture. According to another embodiment of the present invention, the mixture obtained in step (c) comprises from 0.3 to 0.7 wt.-% or from 1.2 to 2.2 wt.-% of said extrusion aid provided in step (b), based on the total dry weight of said mixture. Preferably, the extrusion aid of the foregoing embodiments is a surface-reacted ground natural calcium carbonate (GNCC) having: (i) a volume median grain diameter d 50(vol) of from 1.5 to 12 µm, preferably from 2 to 5 µm or from 6 to 10 µm; and/or (ii) a volume grain diameter d 98(vol) of from 5 to 20 µm, preferably from 8 to 12 µm or from 13 to 18 µm; and/or (iii) a specific surface area of 120 m2/g or less, more preferably from 60 to 120 m2/g, and most preferably from 70 to 105 m2/g, measured using nitrogen and the BET method according to ISO 9277:1995.
- In addition to the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b), the mixture obtained in step (c) may contain one or more suitable additives such as, for example, fillers, dispersants, lubricants, leavenings, nucleating agents, colorants, vitamins, antioxidants, fats, micro nutrients, or flavorants. Some preferred additives will be discussed hereinafter.
- In one embodiment, the mixture obtained in step (c) further comprises added water, preferably in amount of from 0.01 to 15 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%, based on the total dry weight of said mixture. It should be noted that the total amount of water in the mixture obtained in step (c) may be higher than the amount of added water as both the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) may already contain water. In a preferred embodiment, the total water content of the mixture obtained in step (c) is therefore adjusted to from 0.5 to 70 wt.-%, preferably from 1 to 50 wt.-%, more preferably from 2 to 40 wt.-%, and most preferably from 5 to 30 wt.-%, based on the total weight of said mixture.
- According to another embodiment of the present invention, the mixture obtained in step (c) further comprises added whole grains, preferably in amount of from 0.1 to 30 wt.-%, more preferably from 0.5 to 20 wt.-%, and most preferably from 1 to 15 wt.-%, based on the total dry weight of said mixture.
- According to still another embodiment of the present invention, the mixture obtained in step (c) further comprises added sucrose, preferably in amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%, based on the total dry weight of said mixture.
- According to still another embodiment of the present invention, the mixture obtained in step (c) further comprises sodium chloride, preferably in amount of from 0.001 to 5 wt.-%, more preferably from 0.01 to 2 wt.-%, and most preferably from 0.1 to 1 wt.-%, based on the total dry weight of said mixture.
- The mixture obtained in step (c) may also contain unmodified GNCC or PCC additives, i.e. calcium carbonates which are not surface-reacted. Moreover, added unmodified GNCC or PCC may serve as stiffening agent and may have a positive impact on the extrudate if used as packaging material. According to another preferred embodiment, the mixture obtained in step (c) thus comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of unmodified GNCC or PCC, based on the total dry weight of said mixture. Preferably, said unmodified GNCC or PCC is a food-grade GNCC or PCC.
- According to a preferred embodiment of the present invention, said unmodified ground natural or precipitated calcium carbonate is in form of particles having a weight median particle size d 50(wt) of from 0.05 to 10.0 µm, preferably from 0.2 to 5.0 µm, more preferably from 0.4 to 3.0 µm, most preferably from 0.6 to 1.2 µm, and especially 0.7 µm. According to a further embodiment of the present invention, the unmodified ground natural or precipitated calcium carbonate is in form of particles having a top cut particle size d 98(wt) of from 0.15 to 55 µm, preferably from 1 to 40 µm, more preferably from 2 to 25 µm, most preferably from 3 to 15 µm, and especially 4 µm.
- Moreover, the mixture obtained in step (c) may contain added modified starch and/or cellulose, excluding fibrillated cellulose, which may serve, for example, as stabilizer, dispersant, thickener or texture modifier. In one embodiment according to the present invention, the mixture obtained in step (c) therefore contains added modified starch, preferably in an amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%, based on the total dry weight of said mixture.
- In principle, there exist also two ways for combining the foregoing additives with the mixture of step (c), namely separate feeding to the extruder and pre-mixing.
- According to a first embodiment, the additives are fed separately to the extruder inlet, meaning that the raw mixture of step (c) comprising the polysaccharide-containing ground material, the extrusion aid and further additives is formed within the extruder. Side-feeding of additives may also be applied.
- According to a preferred embodiment, the polysaccharide-containing ground material provided in step (a), the extrusion aid provided in step (b) and the further additives are pre-mixed to obtain the mixture of step (c) which is then fed to the extruder inlet. Suitable mixing methods are the same as described hereinabove.
- According to still another embodiment, a combination of separate feeding and pre-mixing may be used to obtain the mixture of step (c) comprising the polysaccharide-containing ground material, the extrusion aid and further additives.
- In step (d) of the process according to the present invention, the mixture obtained in step (c) is puffed by means of an extruder to obtain a puffed polysaccharide-based extrudate.
- As already defined hereinabove, a puffed material in the meaning of the present invention provides the skeletal construct of a porous or foamy structure obtained through porous expansion of a suitable starting formulation. Preferably, expansion is achieved by evaporation of a liquid (e.g. water) embedded in said starting formulation using elevated temperatures and/or rapid pressure decrease.
- In the presently described inventive process, an extruder is used to convert the mixture obtained in step (c) into a puffed material. For this purpose, any known extruder type may be used. The extruder thus may be a single-screw or twin-screw extruder. In a preferred embodiment, the extruder is a twin-screw extruder, most preferably a co-rotating twin-screw extruder.
- The extruder may have various configurations. According to one embodiment of the present invention, the extruder has a screw diameter ranging from 35 to 55 mm, preferably from 40 to 50 mm, for example 44 mm.
- In a more preferred embodiment, the extruder is operated at a screw speed of 60 to 450 rpm with co-rotating twin screws having the following screw configuration. The symbols "/"and "\" are used to indicate the conveying direction and number of the screw elements:
Feeder Mixing Conv. Pressure Temp. Shear Zone Number / Dir. /// / \\ / /// /// // // \ / \ /// Gradient [°] 66 44 poly 66 44 33 44 44 44 33 Length [mm] 66 44 20 66 44 33 15 15 15 33 Offset [°] - - - - 0 0 90 90 90 90 - In the foregoing embodiment, the feeder zone consists of 3 elements DNDL 66/R66 and 1 element DNDL 44/R44, the mixing zone consists of 2 elements of DNDL P45-4/L20, the conveying zone consists of 1 element of DNDL 66/R66, the pressure zone consists of 6 elements of DNDL 44/R44e, the temperature zone consists of 4 elements of DNDL 33/R33, and the shear zone consists of 6 elements: 1 element of DNDL 44/L14.7, 1 element of DNDL 44/R14.7, 1 element of DNDL 44/L14.7 and 3 elements of DNDL 33/L33.
- The characteristics of the extrudate may also be influenced by process parameters, such as moisture, temperature or pressure.
- Therefore, in one embodiment of the inventive process, step (d) is characterized in that the mixture obtained in step (c) is heated to a temperature of from 100°C to 150°C, preferably from 105°C to 140°C, more preferably from 110°C to 135°C, and most preferably from 115°C to 130°C.
- According to another embodiment of the inventive process, step (d) is characterized in that the extruder operates at a minimum pressure of 0.5 MPa, preferably 2.5 MPa, more preferably 3.5 MPa, even more preferably 5 MPa, even more preferably 5.5 MPa, and most preferably 6 MPa. Additionally or alternatively, the extruder operates at a maximum pressure of 10 MPa, preferably 8 MPa, more preferably 7.5 MPa, even more preferably 6 MPa, and most preferably 5 MPa.
- According to another embodiment, suitable die forms and die combinations used at the extruder outlet include (hole diameter in parentheses): 2 × 1-hole die (3.3 mm), 2 × 1-hole die (5.0 mm), 2 × 6-hole die (3.0 mm), 2 × 10-hole die (2.0 mm), 2 × 12-hole die (1.0 mm), 1 × 2-hole die (3.0 mm), 1 × 2-hole die (star shaped), 1 × 2-hole die (tube, 3.0 and 2.0 mm). Preferred die forms and combinations are selected from 2 × 1-hole die (3.3 mm) and 1 × 2-hole die (3.0 mm).
- In combination with any of the foregoing process parameters and configurations, the cross sectional area of the dies may range from 2 to 100 mm2, more preferably from 5 to 50 mm2, and most preferably from 10 to 20 mm2.
- In principle, the puffed polysaccharide-based extrudate obtained in step (d) may thus have any conceivable shape (chips, flakes, spheres, cylinders etc.) depending on the extruder configuration (die form, cutting device, torque, blade speed etc.).
- The product obtainable according to the process of the present invention is a puffed polysaccharide-based material excluding fibrillated cellulose-containing materials (i.e. materials containing microfibrillated cellulose, materials containing nanofibrillated cellulose, materials containing nano-crystalline cellulose and/or fractionated cellulosic materials referenced as noil or crill), meaning that it is produced from a polysaccharide-containing material excluding those containing fibrillated cellulose.
- As indicated hereinabove, the term puffed indicates that the corresponding starting material has been subjected to an expansion step, preferably achieved by evaporation of a liquid (e.g. water) embedded in said starting material using elevated temperatures and/or rapid pressure decrease. In the present case, extrusion cooking is applied.
- Usually, the starting material undergoes no or only little chemical conversion during the expansion process so that, according to a preferred embodiment, the puffed polysaccharide-based material obtainable according to the present invention is a puffed polysaccharide-containing material. The product obtainable according to the inventive process thus contains at least one polysaccharide (excluding fibrillated cellulose), at least one extrusion aid and, optionally, one or more additives selected from fillers, dispersants, lubricants, leavenings, nucleating agents, colorants, flavorants, and the like.
- According to another embodiment of the present invention, the product obtainable according to the inventive process further comprises whole grains, preferably in amount of from 0.1 to 30 wt.-%, more preferably from 0.5 to 20 wt.-%, and most preferably from 1 to 15 wt.-%, based on the total dry weight of said product.
- According to still another embodiment of the present invention, the product obtainable according to the inventive process further comprises sucrose, preferably in amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%, based on the total dry weight of said product.
- According to still another embodiment of the present invention, the product obtainable according to the inventive process further comprises sodium chloride, preferably in amount of from 0.001 to 5 wt.-%, more preferably from 0.01 to 2 wt.-%, and most preferably from 0.1 to 1 wt.-%, based on the total dry weight of said product.
- The product obtainable according to the inventive process may also contain unmodified GNCC or PCC. According to another preferred embodiment, the mixture obtained in step (c) thus comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of unmodified GNCC or PCC, based on the total dry weight of said product. Preferably, said unmodified GNCC or PCC is a food-grade GNCC or PCC.
- The puffed polysaccharide-based material according to the present invention provides improved characteristics compared with conventional extrusion cooked puffed materials, such as material prepared without extrusion aid or with unmodified GNCC or PCC.
For example, the inventive puffed extrusion cooked material provides an increased expansion index which is associated with a lower density. According to a preferred embodiment, the puffed polysaccharide-based material provides an expansion index F of from 5 to 30, preferably from 8 to 25, more preferably from 10 to 20, and most preferably from 12 to 18. - According to another embodiment, the puffed polysaccharide-based material provides a crispness of from 25 to 50 N, preferably from 30 to 48 N, more preferably from 32 to 45 N, and most preferably from 35 to 40 N, measured on a TA.HDplus Texture Analyser from Stable Micro Systems equipped with a Kramer Shear cell with 10 blades.
- In view of the increased expansion index and improved crispness the mouthfeel of corresponding food products is also improved. According to a further embodiment, the inventive process therefore comprises step (e) of processing the puffed polysaccharide-based extrudate obtained in step (d) into:
- (i) a food product for human consumption, preferably breakfast cereals and/or snacks; or
- (ii) a food product for animal consumption, preferably pet food, and more preferably fish food, bird food, dog food and/or cat food.
- Food products for animal consumption further may include food products for farm animals such as cattle, cow, horse, pork, and poultry food.
- Typical processing steps of the foregoing embodiment include deep frying as well as the addition of colorants or flavorants.
- However, as an increased expansion index is not only associated with an improved mouthfeel but also with a lower density, the puffed polysaccharide-based material may also be used as or processed into a packaging material for example in the form of chips, flakes, spheres, cylinders etc. According to another embodiment, the inventive process therefore comprises step (e) of processing the puffed polysaccharide-based extrudate obtained in step (d) into a packaging material. The packaging materials according to the present invention may be biodegradable.
- It is worth noting that the extrusion aid contained in the puffed polysaccharide-based material according to the present invention is a calcium salt and therefore may also serve as a calcium source for dietary purposes.
-
- Figure 1:
- Diameter of the extrudate (snacks)
- Figure 2:
- Diameter of the extrudate (cereals)
- Figure 3:
- Expansion index (snacks)
- Figure 4:
- Expansion index (cereals)
- Figure 5:
- Crispness (snacks)
- Figure 6:
- Photograph of extrudate (standard cereal)
- Figure 7:
- Photograph of extrudate (cereals prepared with 0.5% of SRCC2)
- Figure 8:
- Stereo microscope (SM) image of the cross section of extrudate (standard snack)
- Figure 9:
- Stereo microscope (SM) image of the cross section of extrudate (cereals prepared with 0.5% of SRCC3)
- The scope and interest of the invention may be better understood on basis of the following examples which are intended to illustrate embodiments of the present invention. However, they are not to be construed to limit the scope of the claims in any manner whatsoever.
- In the following, the measuring methods for the parameters defined in the present application and used in the following examples are described.
- The volume determined median particle size d 50(vol) and the volume determined top cut particle size d 98(vol) were evaluated using a Malvern Mastersizer 2000 Laser Diffraction System (Malvern Instruments Plc., Great Britain). The raw data obtained by the measurement was analysed using the Fraunhofer theory without specified refractive index, with an absorption index of 0.005. The methods and instruments are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments.
- The weight determined median particle size d 50(wt) was measured by the sedimentation method, which is an analysis of sedimentation behaviour in a gravimetric field. The measurement was made with a Sedigraph™ 5120 of Micromeritics Instrument Corporation, USA. The method and the instrument are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments. The measurement was carried out in an aqueous solution of 0.1 wt.-% Na4P2O7. The samples were dispersed using a high speed stirrer and sonicated.
- The specific surface area was measured via the BET method according to
ISO 9277:1995 using nitrogen, following conditioning of the sample by heating at 250°C for a period of 30 minutes. Prior to such measurements, the sample was filtered within a Büchner funnel, rinsed with deionised water and dried overnight at 90 to 100°C in an oven. Subsequently, the dry cake was ground thoroughly in a mortar and the resulting powder was placed in a moisture balance at 130°C until a constant weight was reached. - The specific pore volume was measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 µm. The equilibration time used at each pressure step was 20 seconds. The sample material was sealed in a 5 cm3 chamber powder penetrometer for analysis. The data were corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Comp (Gane, P.A.C., Kettle, J.P., Matthews, G.P. and Ridgway, C.J., "Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations", Industrial and Engineering Chemistry Research, 35(5), 1996, pp. 1753-1764).
- The expansion index F is a measure to describe the cross-sectional expansion of an extrudate after passing the outlet of an extruder. The expansion index used herein is defined as:
- Samples are weighed so that equally defined portions are obtained. The amount must be such that at least half of the Kramer shear cell is filled volumetrically. The Kramer shear cell simulates a single bite on a sample and thus provides information about bite-behaviour, crispness and consistency. The 10 blades are moved with constant velocity through the sample, compressing, shearing and extruding the sample through the slotted base plate. Measuring of multiple blades at the same time results in measuring at different places in the sample (resistance in Newtons) for levelling out local structural differences. Measuring parameters are set out in the table below.
T.A. Settings & Parameters Type of test: pressure Velocity for : 10.00 mm/s Velocity test: 8.00 mm/s Velocity back: 10.00 mm/s Target parameter: strain Strength: 100.0 g Path : 5.000 mm Strain: 105.0 % Release : AUTO (force) Release force : 5.0 g Tool: HDP/ KS 10;KRAMER SHEAR CELL 10 BLADECharge: C-DP-0749-0.5 % Measuring points per second : 500 - The following mineral materials are used as extrusion aids or as corresponding reference materials.
- SRCC1 had a d 50(vol) = 6.6 µm, d 98(vol) = 15.1 µm, SSA = 144 m2/g with an intra-particle intruded specific pore volume of 0.811 cm3/g (for the pore diameter range of 0.004 to 0.23 µm).
- SRCC1 was obtained by preparing 450 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground marble calcium carbonate from Hustadmarmor, Norway, having a mass based median particle size distribution of 90 % less than 2 µm, as determined by sedimentation, such that a solids content of 16 wt.-%, based on the total weight of the aqueous suspension, is obtained.
- Whilst mixing the slurry, 47.1 kg phosphoric acid were added in form of an aqueous solution containing 30 wt.-% phosphoric acid to said suspension over a period of 15 minutes at a temperature of 70°C. After the addition of the acid, the slurry was stirred for additional 5 minutes, before removing it from the vessel and drying.
- SRCC2 had a d 50(vol) = 2.98 µm, d 98(vol) = 10.64 µm, SSA = 97.55 m2/g with an intra-particle intruded specific pore volume of 0.723 cm3/g (for the pore diameter range of 0.004 to 0.18 µm).
- SRCC2 was obtained by preparing 10 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground limestone calcium carbonate from Omya SAS, Orgon, having a mass based median particle size distribution of 90 % less than 1 µm, as determined by sedimentation, such that a solids content of 10 wt.-%, based on the total weight of the aqueous suspension, is obtained.
- Whilst mixing the slurry, 2.7 kg phosphoric acid was added in form of an aqueous solution containing 20 wt.-% phosphoric acid to said suspension over a period of 44 minutes at a temperature of 70°C. After the addition of the acid, the slurry was stirred for additional 5 minutes, before removing it from the vessel and drying.
- SRCC3 had a d 50(vol) = 6.13 µm, d 98(vol) = 15 µm, SSA = 55.5 m2/g with an intra-particle intruded specific pore volume of 0.739 cm3/g (for the pore diameter range of 0.004 to 0.41 µm).
- A calcium carbonate suspension is prepared by adding water and undispersed limestone (ground under wet conditions in water, optionally in the presence of a food approved dispersing or grinding aid such as monopropyleneglycol (MPG)) having a d 50(wt) of 3 µm, wherein 33 wt.-% of particles have a diameter of less than 2 µm in a 20 L stainless steel reactor, such that the aqueous suspension obtained has a solids content corresponding to 16 wt.-% by dry weight relative to the total suspension weight. The temperature of this suspension is thereafter is brought to and maintained at 70°C. Under stirring at approximately 1 000 rpm such that an essential laminar flow is established, phosphoric acid in the form of a 30 % solution is added to the calcium carbonate suspension through a separate funnel over a period of 10 minutes in an amount corresponding to 30 % by weight on dry calcium carbonate weight. Following this addition, the suspension is stirred for an additional 5 minutes. The resulting suspension was allowed to settle overnight, and the SRCC had a specific surface area of 36 m2/g, a d 50(vol) of 9.3 µm (Malvern) and d 98(vol) of 23.5 µm (Malvern).
- A calcium carbonate suspension is prepared by adding water and undispersed marble (ground under wet conditions in water, optionally in the presence of a food approved dispersing or grinding aid such as monopropyleneglycol (MPG)) having a d 50(wt) of 3.5 µm, wherein 33 wt.-% of particles have a diameter of less than 2 µm in a 20 L stainless steel reactor, such that the aqueous suspension obtained has a solids content corresponding to 16 wt.-% by dry weight relative to the total suspension weight. The temperature of this suspension is thereafter is brought to and maintained at 70°C. Under stirring at approximately 1 000 rpm such that an essential laminar flow is established, phosphoric acid in the form of a 30 % solution is added to the calcium carbonate suspension through a separate funnel over a period of 10 minutes in an amount corresponding to 30 % by weight on dry calcium carbonate weight. Following this addition, the suspension is stirred for an additional 5 minutes. The resulting suspension was allowed to settle overnight, and the SRCC had a specific surface area of 46 m2/g, a d 50(vol) of 9.5 µm (Malvern) and d 98(vol) of 18.9 µm (Malvern).
- A calcium carbonate suspension is prepared by adding water and undispersed marble of (ground under wet conditions in water, optionally in the presence of a food approved dispersing or grinding aid such as monopropyleneglycol (MPG)) having a d 50(wt) of 2 µm in a 20 L stainless steel reactor, such that the aqueous suspension obtained has a solids content corresponding to 16 wt.-% by dry weight relative to the total suspension weight. The temperature of this suspension is thereafter is brought to and maintained at 70°C. Under stirring at approximately 1 000 rpm such that an essential laminar flow is established phosphoric acid in the form of a 30% solution is added to the calcium carbonate suspension through a separate funnel over a period of 10 minutes in an amount corresponding to 50% by weight on dry calcium carbonate weight. Following this addition, the suspension is stirred for an additional 5 minutes. The resulting suspension was allowed to settle overnight, and the SRCC had a specific surface area of 71 m2/g, a d 50(vol) of 10.6 µm (Malvern) and d 98(vol) of 21.8 µm (Malvern).
- GNCC1 was a food-grade high purity natural calcium carbonate, commercially available from Omya International AG, Switzerland, d 50(wt) = 5.5 µm.
- For the purpose of the following examples, commercially available standard corn flour was purchased from Bäko eG, Germany. Roland Mehl Typ 550 and Grüner Roland Typ 1050 were used as wheat cereals and were purchased from Bremer Rolandmühle Erling GmbH & Co. KG, Germany.
- Twin-screw extruder DNDL-44, from Bühler AG, Uzwil, Switzerland, with the following parts:
-
- ▪ Number of housings: 5 (where 4 D = 0.176 m)
- ▪ Housings separately or connectedly heatable or coolable
- ▪ Heating medium: steam
- ▪ Cooling medium: water
- ▪ Processing length: 20 D (1 D = 0.044 m)
-
- ▪ Twin-screw
- ▪ Worm gear shaft rotating in the same direction
- ▪ Twin-screw diameter: 44 mm
- ▪ Twin-screw length (without coupling): 0.88 m (corresponds to 20 D)
- ▪ Screw speed: 60 to 450 rpm
- ▪ Standard screw configuration:
- The feeder zone consisted of 3 elements DNDL 66/R66 and 1 element DNDL 44/R44, the mixing zone consisted of 2 elements of DNDL P45-4/L20, the conveying zone consisted of 1 element of DNDL 66/R66, the pressure zone consisted of 6 elements of DNDL 44/R44e, the temperature zone consisted of 4 elements of DNDL 33/R33, and the shear zone consisted of 6 elements: 1 element of DNDL 44/L14.7, 1 element of DNDL 44/R14.7, 1 element of DNDL 44/L14.7 and 3 elements of DNDL 33/L33.
-
- ▪ Movable
- ▪ Cutter head with 4 blades
-
Die form Hole diam. Cross-sect. area Die form Hole diam. Cross-sect. area 2 × 1-hole 3.3 mm 17.1 mm 21 × 2-hole 3.0 mm 14.1 mm 22 × 1-hole 5.0 mm 39.2 mm 21 × 2-hole star shaped ca. 60 mm 22 × 6-hole 3.0 mm 84.8 mm 22 × 10-hole 2.0 mm 62.8 mm 21 × 2-hole (tube) 3.0 mm 3.9 mm 22 × 12-hole 1.0 mm 18.8mm2 2.0 mm -
- ▪ Twin-screw feed device
- ▪ Volumetric feed (metering unit with container)
-
▪ Product: snacks
▪ Final screw: cone-shaped
▪ Die: 1 × 2-hole (diameter: 3 mm)
▪ Recipe:Ingredients Corn flour Sugar Salt SRCC Total Standard Amount % 98.00 1.00 1.00 0.00 100.00 Amount kg 29.40 0.30 0.30 0.00 30.00 SRCC 0.5 % Amount % 97.50 1.00 1.00 0.50 100.00 Amount kg 14.63 0.15 0.15 0.08 15.00 SRCC 1.5 % Amount % 96.50 1.00 1.00 1.50 100.00 Amount kg 14.48 0.15 0.15 0.23 15.00 SRCC 2.0 % Amount % 96.00 1.00 1.00 2.00 100.00 Amount kg 14.40 0.15 0.15 0.30 15.00 SRCC 5.0 % Amount % 93.00 1.00 1.00 5.00 100.00 Amount kg 13.95 0.15 0.15 0.75 15.00 SRCC 10.0 % Amount % 88.00 1.00 1.00 10.00 100.00 Amount kg 13.20 0.15 0.15 1.50 15.00
▪ Process parameters:Sample No. Standard SRCC1 0.5% SRCC1 1.5% SRCC2 0.5% SRCC2 1.5% Torque [%] 44 46 52 47 47 Speed [%] 50 50 50 50 50 Blade speed [%] 33 33 33 33 33 H2O addition [kg/h] 3.9 3.9 3.9 3.9 3.9 Product dosing [kg/h] 33 33 33 33 33 Pressure [bar] 45-50 45-50 50 45-50 45-50 Temp. module 2 [°C] 100 100 100 100 100 Temp. module 3 [°C] 110 110 110 110 110 Temp. module 4 [°C] 125 125 125 125 125 Temp. module 5 [°C] 125 125 125 125 125 Sample No. SRCC3 0.5% SRCC3 1.5 % SRCC3 2.0 % SRCC3 5.0 % SRCC3 10.0 % Torque [%] 46 49 50 54 67 Speed [%] 50 50 50 50 50 Blade speed [%] 33 33 33 33 33 H2O addition [kg/h] 3.9 3.9 3.9 3.9 3.9 Product dosing [kg/h] 33 33 33 33 33 Pressure [bar] 45-50 50 51 51-55 30 Temp. module 2 [°C] 100 100 100 100 100 Temp. module 3 [°C] 110 110 110 110 110 Temp. module 4 [°C] 125 125 125 125 125 Temp. module 5 [°C] 125 125 125 125 125 -
▪ Product: cereals
▪ Final screw: cone-shaped
▪ Die: 1 × 2-hole (diameter: 3 mm)
▪ Recipe:Ingredients Wheat flour Wheat whole grain Sugar Salt SRCC Total Standard Amount % 82.50 10.00 7.00 0.50 0.00 100.00 Amount kg 24.75 3.00 2.10 0.15 0.00 30.00 SRCC 0.5 % Amount % 82.00 10.00 7.00 0.50 0.50 100.00 Amount kg 12.30 1.50 1.05 0.08 0.08 15.00 SRCC 1.5 % Amount % 81.00 10.00 7.00 0.50 1.50 100.00 Amount kg 12.15 1.50 1.05 0.08 0.23 15.00 SRCC 2.0% Amount % 80.50 10.00 7.00 0.50 2.00 100.00 Amount kg 12.08 1.50 1.05 0.08 0.30 15.00 SRCC 5.0 % Amount % 78.50 10.00 7.00 0.50 5.00 100.00 Amount kg 11.78 1.50 1.05 0.08 0.75 15.00 SRCC 10.0 % Amount % 72.78 10.00 7.00 0.50 10.00 100.00 Amount kg 10.88 1.50 1.05 0.08 1.50 15.00
▪ Process parameters:Sample No. Standard SRCC1 0.5 % SRCC1 1.5 % SRCC2 0.5 % SRCC2 1.5 % Torque [%] 40 55 57 54 53 Speed [%] 52 52 52 52 52 Blade speed [%] 34 34 34 34 34 H2O addition [kg/h] 1.2 1.2 1.2 1.2 1.2 Product dosing [kg/h] 35 35 35 35 35 Pressure [bar] 41 53 55-60 55 55 Temp. module 2 [°C] 100 100 100 100 100 Temp. module 3 [°C] 110 110 110 110 110 Temp. module 4 [°C] 125 125 125 125 125 Temp. module 5 [°C] 135 135 135 135 135 Sample No. SRCC3 0.5% SRCC3 1.5 % SRCC3 2.0% SRCC3 5.0% SRCC3 10.0 % Torque [%] 46 51 54 56 54 Speed [%] 52 52 52 52 52 Blade speed [%] 34 34 34 34 34 H2O addition [kg/h] 1.2 1.2 1.2 1.2 1.2 Product dosing [kg/h] 35 35 35 35 35 Pressure [bar] 48 42 53 54 38 Temp. module 2 [°C] 100 100 100 100 100 Temp. module 3 [°C] 110 110 110 110 110 Temp. module 4 [°C] 125 125 125 125 125 Temp. module 5 [°C] 135 135 135 135 135 -
Figures 1 to 5 show the results for the diameter of the extrudate (Fig. 1 : snacks,Fig. 2 : cereals), the expansion index (Fig. 3 : snacks,Fig. 4 : cereals), and the crispness of snacks (Fig. 5 ). -
Figures 6 and7 show photographs of standard cereals (Fig. 6 ) and of cereals prepared in the presence of 0.5 % SRCC2 (Fig. 7 ). -
Figures 8 and9 show stereo microscope (SM) images of the cross section of a standard snack (Fig. 8 ) and of a snack that was prepared in the presence of SRCC3 - 0.5 % (Fig.9 ). The images were made with a Leica MZ16A stereo microscope and a Leica DFC 320 camera and angled light illumination to show the structure of the samples. -
- The results of the present examples indicate an increased expansion index (F) and improved crispness ( TA.HDplus Texture Analyser ) for the products prepared according to the inventive process compared with the samples prepared from standard calcium carbonate (GNCC1) which were prepared analogously (see
Figures 1 to 5 ). Furthermore, the organoleptic panel test revealed improved surface textures and crispness (see the foregoing tables).
Feeder | Mixing | Conv. | Pressure | Temp. | Shear Zone | |||||
Amount / Dir. | /// | / | \\ | / | /// /// | // // | \ | / | \ | /// |
Gradient [°] | 66 | 44 | poly | 66 | 44 | 33 | 44 | 44 | 44 | 33 |
Length [mm] | 66 | 44 | 20 | 66 | 44 | 33 | 15 | 15 | 15 | 33 |
Offset [°] | - | - | - | - | 0 | 0 | 90 | 90 | 90 | 90 |
Claims (17)
- A process for the production of a puffed polysaccharide-based material, the process comprising the following steps:(a) providing at least one polysaccharide-containing ground material excluding fibrillated cellulose-containing materials;(b) providing at least one extrusion aid;(c) combining the polysaccharide-containing ground material provided in step (a) and the extrusion aid provided in step (b) to obtain a mixture; and(d) puffing the mixture obtained in step (c) by means of an extruder to obtain a puffed polysaccharide-based extrudate;characterized in that said extrusion aid provided in step (b) is a surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC) treated with CO2 and one or more H3O+ ion donors and wherein the CO2 is formed in situ by the H3O+ ion donors treatment and/or is supplied from an external source.
- The process according to claim 1, characterized in that:(i) the polysaccharide is a homopolysaccharide, preferably starch; and/or(ii) the polysaccharide-containing ground material provided in step (a) of claim 1 comprises barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof, preferably the polysaccharide-containing ground material is selected from groat, semolina or flour of barley, corn (maize), oats, rice, rye, spelt, wheat, amaranth, quinoa, millet or mixtures thereof, and more preferably the polysaccharide-containing ground material is corn (maize) flour, wheat flour, nut flour or a mixture thereof.
- The process according to any of claims 1 to 2, characterized in that the one or more H3O+ ion donors are selected from:(i) strong acids having a pKa of 0 or less at 20°C; and/or(ii) medium-strong acids having a pKa value from 0 to 2.5 at 20°C; and/or(iii) weak acids having a pKa of greater than 2.5 and less than or equal to 7 at 20°C, associated with the ionisation of its first available hydrogen, wherein a corresponding anion is formed on loss of this first available hydrogen capable of forming a water-soluble calcium salt, and wherein at least one water-soluble salt, which in the case of a hydrogen-containing salt has a pKa of greater than 7 at 20°C, associated with the ionisation of the first available hydrogen, and the salt anion of which is capable of forming water-insoluble calcium salts, is additionally provided.
- The process according to any of claims 1 to 2, characterized in that the surface-reacted calcium carbonate is obtained by a process comprising the following steps:(a) providing a suspension of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC);(b) adding at least one acid having a pKa value of 0 or less at 20°C, or having a pKa value from 0 to 2.5 at 20°C to the suspension provided in step (a); and(c) treating the suspension provided in step (a) with CO2 before, during or after step (b).
- The process according to any of claims 1 to 2, characterized in that the surface-reacted calcium carbonate is obtained by a process comprising the following steps:(a) providing ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC);(b) providing at least one water-soluble acid;(c) providing gaseous CO2; and(d) contacting said GNCC or PCC provided in step (a), the at least one acid provided in step (b) and the gaseous CO2 provided in step (c);characterized in that (i) the at least one acid provided in step (b) has a pKa of greater than 2.5 and less than or equal to 7 at 20°C, associated with the ionisation of its first available hydrogen, and a corresponding anion is formed on loss of this first available hydrogen capable of forming a water-soluble calcium salt; and (ii) following contacting the at least one water-soluble acid provided in step (b) and the GNCC or PCC provided in step (a), at least one water-soluble salt, which in the case of a hydrogen-containing salt has a pKa of greater than 7 at 20°C, associated with the ionisation of the first available hydrogen, and the salt anion of which is capable of forming water-insoluble calcium salts, is additionally provided.
- The process according to any of claims 1 to 5, characterized in that:(i) the natural calcium carbonate is selected from the group consisting of marble, chalk, dolomite, limestone and mixtures thereof; and/or(ii) the precipitated calcium carbonate comprises aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof.
- The process according to any of claims 1 to 6, characterized in that the extrusion aid has:(i) a volume median grain diameter d 50(vol) of from 1 to 75 µm, preferably from 1.5 to 50 µm, more preferably from 2 to 40 µm, and most preferably from 2.5 to 7.0 µm; and/or(ii) a volume grain diameter d 98(vol) of from 2 to 150 µm, preferably from 4 to 100 µm, more preferably from 6 to 80 µm, even more preferably from 8 to 60 µm, and most preferably from 10 to 30 µm.
- The process according to any of claims 1 to 7, characterized in that the extrusion aid has a specific surface area of from 15 to 200 m2/g, preferably from 27 to 180 m2/g, more preferably from 30 to 160 m2/g, even more preferably from 45 to 150 m2/g, and most preferably from 48 to 140 m2/g, measured using nitrogen and the BET method according to ISO 9277:1995.
- The process according to any of claims 1 to 8, characterized in that the mixture obtained in step (c) of claim 1 comprises from 0.01 to 10 wt.-%, preferably from 0.05 to 5 wt.-%, more preferably from 0.1 to 2 wt.-%, and most preferably from 0.2 to 1.8 wt.-% of the extrusion aid provided in step (b) of claim 1, based on the total dry weight of said mixture.
- The process according to any of claims 1 to 9, characterized in that in step (d) of claim 1:(i) the mixture obtained in step (c) of claim 1 is heated to from 100°C to 150°C, preferably from 105°C to 140°C, more preferably from 110°C to 135°C, and most preferably from 115°C to 130°C; and/or(ii) the extruder operates at a minimum pressure of 0.5 MPa, preferably 2.5 MPa, more preferably 3.5 MPa, even more preferably 5 MPa, even more preferably 5.5 MPa, and most preferably 6 MPa; and/or(iii) the extruder operates at a maximum pressure of 10 MPa, preferably 8 MPa, more preferably 7.5 MPa, even more preferably 6 MPa, and most preferably 5 MPa.
- The process according to any of claims 1 to 10, characterized in that the mixture obtained in step (c) of claim 1 further comprises the following additives:(i) water, preferably in amount of from 0.01 to 15 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%; and/or(ii) whole grains, preferably in amount of from 0.1 to 30 wt.-%, more preferably from 0.5 to 20 wt.-%, and most preferably from 1 to 15 wt.-%; and/or(iii) sucrose, preferably in amount of from 0.01 to 20 wt.-%, more preferably from 0.1 to 10 wt.-%, and most preferably from 0.2 to 5 wt.-%; and/or(iv) sodium chloride, preferably in amount of from 0.001 to 5 wt.-%, more preferably from 0.01 to 2 wt.-%, and most preferably from 0.1 to 1 wt.-%;each based on the total dry weight of said mixture.
- The process according to any of claims 1 to 11, characterized in that the process further comprises step (e) of processing the puffed polysaccharide-based extrudate obtained in step (d) of claim 1 into:(i) a food product for human consumption, preferably breakfast cereals and/or snacks; or(ii) a food product for animal consumption, preferably pet food, and more preferably fish food, bird food, dog food and/or cat food; or(iii) a packaging material.
- Use of a surface-reacted calcium carbonate as extrusion aid for the production of a puffed polysaccharide-based material excluding fibrillated cellulose-containing materials, wherein the surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC) treated with CO2 and one or more H3O+ ion donors and wherein the CO2 is formed in situ by the H3O+ ion donors treatment and/or is supplied from an external source.
- The use according to claim 13, characterized in that the extrusion aid has:(i) a volume median grain diameter d 50(vol) of from 1 to 75 µm, preferably from 1.5 to 50 µm, more preferably from 2 to 40 µm, and most preferably from 2.5 to 7.0 µm; and/or(ii) a volume grain diameter d 98(vol) of from 2 to 150 µm, preferably from 4 to 100 µm, more preferably from 6 to 80 µm, even more preferably from 8 to 60 µm, and most preferably from 10 to 30 µm.
- The use according to any of claims 13 to 14, characterized in that the extrusion aid has a specific surface area of from 15 to 200 m2/g, preferably from 27 to 180 m2/g, more preferably from 30 to 160 m2/g, even more preferably from 45 to 150 m2/g, and most preferably from 48 to 140 m2/g, measured using nitrogen and the BET method according to ISO 9277:1995.
- A puffed polysaccharide-based material excluding fibrillated cellulose-containing materials, obtainable according to the process defined in any of claims 1 to 12.
- The puffed polysaccharide-based material according to claim 16, characterized in that said material provides:(i) an expansion index F of from 5 to 30, preferably from 8 to 25, more preferably from 10 to 20, and most preferably from 12 to 18; and/or(ii) a crispness of from 25 to 50 N, preferably from 30 to 48 N, more preferably from 32 to 45 N, and most preferably from 35 to 40 N, measured on a TA.HDplus Texture Analyser from Stable Micro Systems equipped with a Kramer Shear cell with 10 blades.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
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PL16176267T PL3260419T3 (en) | 2016-06-24 | 2016-06-24 | Surface-reacted calcium carbonate as extrusion aid |
TR2018/15833T TR201815833T4 (en) | 2016-06-24 | 2016-06-24 | Surface reactive calcium carbonate as extrusion support. |
EP16176267.9A EP3260419B1 (en) | 2016-06-24 | 2016-06-24 | Surface-reacted calcium carbonate as extrusion aid |
ES16176267T ES2697908T3 (en) | 2016-06-24 | 2016-06-24 | Calcium carbonate surface treated as an extrusion adjuvant |
CA3028530A CA3028530A1 (en) | 2016-06-24 | 2017-06-14 | Surface-reacted calcium carbonate as extrusion aid |
PCT/EP2017/064579 WO2017220412A1 (en) | 2016-06-24 | 2017-06-14 | Surface-reacted calcium carbonate as extrusion aid |
JP2018567274A JP2019527542A (en) | 2016-06-24 | 2017-06-14 | Surface-reacted calcium carbonate as an extrusion aid |
BR112018074715-7A BR112018074715A2 (en) | 2016-06-24 | 2017-06-14 | process for producing an expanded polysaccharide-based material, use of a surface-reacted calcium carbonate, and expanded polysaccharide-based material |
CN201780039208.6A CN109415221B (en) | 2016-06-24 | 2017-06-14 | Surface-reacted calcium carbonate as extrusion aid |
RU2019101791A RU2019101791A (en) | 2016-06-24 | 2017-06-14 | SURFACE-TREATED CALCIUM CARBONATE AS AN EXTRUSION-PROMOTING ADDITIVE |
US16/310,504 US11576410B2 (en) | 2016-06-24 | 2017-06-14 | Surface-reacted calcium carbonate as extrusion aid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP16176267.9A EP3260419B1 (en) | 2016-06-24 | 2016-06-24 | Surface-reacted calcium carbonate as extrusion aid |
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EP3260419A1 EP3260419A1 (en) | 2017-12-27 |
EP3260419B1 true EP3260419B1 (en) | 2018-08-15 |
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EP16176267.9A Active EP3260419B1 (en) | 2016-06-24 | 2016-06-24 | Surface-reacted calcium carbonate as extrusion aid |
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US (1) | US11576410B2 (en) |
EP (1) | EP3260419B1 (en) |
JP (1) | JP2019527542A (en) |
CN (1) | CN109415221B (en) |
BR (1) | BR112018074715A2 (en) |
CA (1) | CA3028530A1 (en) |
ES (1) | ES2697908T3 (en) |
PL (1) | PL3260419T3 (en) |
RU (1) | RU2019101791A (en) |
TR (1) | TR201815833T4 (en) |
WO (1) | WO2017220412A1 (en) |
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EP3400810A1 (en) * | 2017-05-11 | 2018-11-14 | Omya International AG | Surface-reacted calcium carbonate in food |
EP3501298A1 (en) * | 2017-12-22 | 2019-06-26 | Omya International AG | Surface-reacted calcium carbonate as extrusion aid |
US20220264930A1 (en) * | 2019-07-23 | 2022-08-25 | H.J. Heinz Company Brands Llc | Shelf-stable, extruded food products |
SK9416Y1 (en) * | 2021-04-08 | 2022-01-26 | Titan Construct engineering s.r.o. | Biodegradable single-use packaging especially for food, method of its production and form for production of biodegradable single-use packaging |
Family Cites Families (20)
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JPS63196230A (en) | 1987-02-10 | 1988-08-15 | Sanyo Koka Cola Botoringu Kk | Production of snack foods useful for maintaining health |
US5366748A (en) | 1992-09-14 | 1994-11-22 | The Procter & Gamble Company | Method of production of extruded cereal grain-based food products having improved qualities |
US6136359A (en) | 1996-01-16 | 2000-10-24 | The Procter & Gamble Company | Fried snack dough composition and method of preparing a fried snack product |
US6010732A (en) | 1997-11-04 | 2000-01-04 | General Mills, Inc. | Grain based extruded product and process of making |
FR2787802B1 (en) | 1998-12-24 | 2001-02-02 | Pluss Stauffer Ag | NOVEL FILLER OR PIGMENT OR MINERAL TREATED FOR PAPER, ESPECIALLY PIGMENT CONTAINING NATURAL CACO3, METHOD FOR MANUFACTURING SAME, COMPOSITIONS CONTAINING THEM, AND APPLICATIONS THEREOF |
DE60040843D1 (en) * | 2000-05-01 | 2009-01-02 | Nestle Sa | Production method of a cereal bar |
US6913775B2 (en) | 2000-05-05 | 2005-07-05 | General Mills, Inc. | Cooked cereal dough products fortified with calcium and method of preparation |
FR2852600B1 (en) | 2003-03-18 | 2005-06-10 | NEW MINERAL PIGMENT CONTAINING CALCIUM CARBONATE, AQUEOUS SUSPENSION CONTAINING SAME AND USES THEREOF | |
FR2871474B1 (en) | 2004-06-11 | 2006-09-15 | Omya Development Ag | NEW DRY MINERAL PIGMENT CONTAINING CALCIUM CARBONATE, AQUEOUS SUSPENSION CONTAINING IT AND USES THEREOF |
JPWO2008004512A1 (en) * | 2006-07-03 | 2009-12-03 | 不二製油株式会社 | Production method of high protein soy snack food |
CN101451023B (en) * | 2007-12-04 | 2012-05-09 | 比亚迪股份有限公司 | Surface modified nano calcium carbonate and polychloroethylene plastisol thereof |
EP2070991B1 (en) | 2007-12-12 | 2010-09-08 | Omya Development AG | Process to make surface-reacted precipitated calcium carbonate |
EP2194103A1 (en) * | 2008-12-04 | 2010-06-09 | Omya Development Ag | Process for manufacturing calcium carbonate materials having a particle surface with improved adsorption properties |
DK2264108T3 (en) * | 2009-06-15 | 2012-05-29 | Omya Development Ag | Process for preparing a calcium carbonate that has reacted to the surface using a weak acid |
PT2264109E (en) * | 2009-06-15 | 2012-05-09 | Omya Development Ag | Process for preparing surface-reacted calcium carbonate and its use |
US20120064209A1 (en) * | 2010-09-15 | 2012-03-15 | Frito-Lay North America, Inc. | Protein Ingredient Selection and Manipulation for the Manufacture of Snack Foods |
CN102051071A (en) * | 2010-11-04 | 2011-05-11 | 东北林业大学 | Method for preparing acid-proof calcium carbonate filler fit for making paper with old newspaper deinked pulp with high lignin content and filling paper thereof |
JP2015521864A (en) * | 2012-07-18 | 2015-08-03 | ネステク ソシエテ アノニム | Extruded food |
CN104068345B (en) * | 2013-03-29 | 2017-08-25 | 成都市棒棒娃实业有限公司 | Sandwich expanded rice cracker volume and preparation method thereof |
CN105495354A (en) * | 2015-12-02 | 2016-04-20 | 郑州荣利达生物科技有限公司 | Fried and puffed food and preparation method thereof |
-
2016
- 2016-06-24 EP EP16176267.9A patent/EP3260419B1/en active Active
- 2016-06-24 TR TR2018/15833T patent/TR201815833T4/en unknown
- 2016-06-24 ES ES16176267T patent/ES2697908T3/en active Active
- 2016-06-24 PL PL16176267T patent/PL3260419T3/en unknown
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2017
- 2017-06-14 CN CN201780039208.6A patent/CN109415221B/en active Active
- 2017-06-14 WO PCT/EP2017/064579 patent/WO2017220412A1/en active Application Filing
- 2017-06-14 BR BR112018074715-7A patent/BR112018074715A2/en not_active Application Discontinuation
- 2017-06-14 JP JP2018567274A patent/JP2019527542A/en not_active Ceased
- 2017-06-14 CA CA3028530A patent/CA3028530A1/en not_active Abandoned
- 2017-06-14 US US16/310,504 patent/US11576410B2/en active Active
- 2017-06-14 RU RU2019101791A patent/RU2019101791A/en not_active Application Discontinuation
Non-Patent Citations (1)
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None * |
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ES2697908T3 (en) | 2019-01-29 |
CN109415221A (en) | 2019-03-01 |
US11576410B2 (en) | 2023-02-14 |
US20190320691A1 (en) | 2019-10-24 |
BR112018074715A2 (en) | 2019-03-12 |
CA3028530A1 (en) | 2017-12-28 |
WO2017220412A1 (en) | 2017-12-28 |
CN109415221B (en) | 2021-06-04 |
TR201815833T4 (en) | 2018-11-21 |
JP2019527542A (en) | 2019-10-03 |
RU2019101791A (en) | 2020-07-24 |
PL3260419T3 (en) | 2019-01-31 |
EP3260419A1 (en) | 2017-12-27 |
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